Ci a ion: Bubulinca, C.; Kazan se a,
N.E.; Pechanco a, V.; Joseph, N.; Fei,
H.; Venhe , M.; I anichenko, A.; Saha,
P. De elopmen o All-Solid-S a e
Li-Ion Ba e ies: F om Key Technical
A eas o Comme cial Use. Ba e ies
2023,9, 157. h ps://doi.o g/
10.3390/ba e ies9030157
Academic Edi o : A sushi Nagai
Recei ed: 15 Decembe 2022
Re ised: 14 Feb ua y 2023
Accep ed: 24 Feb ua y 2023
Published: 1 Ma ch 2023
Copy igh : © 2023 by he au ho s.
Licensee MDPI, Basel, Swi ze land.
This a icle is an open access a icle
dis ibu ed unde he e ms and
condi ions o he C ea i e Commons
A ibu ion (CC BY) license (h ps://
c ea i ecommons.o g/licenses/by/
4.0/).
ba e ies
Re iew
De elopmen o All-Solid-S a e Li-Ion Ba e ies: F om Key
Technical A eas o Comme cial Use
Cons an in Bubulinca 1,*, Na alia E. Kazan se a 1, Vie a Pechanco a 1,2 , Nikhi ha Joseph 1, Haojie Fei 1,
Ma iana Venhe 1, Anna I anichenko 1and Pe Saha 1,2
1Cen e o Polyme Sys ems, Tomas Ba a Uni e si y in Zlín, T . T. Ba i 5678, 760 01 Zlin, Czech Republic
2Uni e si y Ins i u e, Tomas Ba a Uni e si y in Zlín, Nad O ˇcí nou IV 3685, 760 01 Zlín, Czech Republic
*Co espondence: [email p o ec ed]
Abs ac :
Inno a ion in he design o Li-ion echa geable ba e ies is necessa y o o e come sa e y
conce ns and mee ene gy demands. In his ega d, a new gene a ion o Li-ion ba e ies (LIBs) in
he o m o all-solid-s a e ba e ies (ASSBs) has been de eloped, a ac ing a g ea deal o a en ion
o hei high-ene gy densi y and excellen mechanical-elec ochemical s abili y. This e iew de-
sc ibes he cu en s a e o esea ch and de elopmen on ASSB echnology. To his end, s udy o
he li e a u e and pa en s as well as ma ke analysis o e he las wo decades we e ca ied ou ,
highligh ing how scien i ic achie emen s ha e in o med he applica ion o comme cially p o i able
ASSBs. Analyzing he pa en s egis e ed o e he pas 20 yea s e ealed ha he numbe o hem had
inc eased exponen ially- om only ew pe yea in ea ly 2000 o mo e han 342 in 2020. Published
li e a u e and pa en s on he opic decla e a solid-s a e elec oly e (SSE) o be he main componen o
ASSBs, and mos pa en ed examples a e e e ed o as solid ino ganic elec oly es (SIEs), ollowed by
solid polyme elec oly es (SPEs) and solid hyb id elec oly es (SHEs) in popula i y. In es iga ion o
company websi es, social media p o iles, epo s, and academic publica ions iden i ied 93 companies
associa ed wi h ASSBs. A lis o leading businesses in he solid-s a e ba e y sec o was compiled, ou
o which 36 p o ided in o ma ion on he ASSB uni s in hei p oduc po olio o de ailed analysis.
Keywo ds:
all-solid-s a e ba e ies; solid-s a e elec oly e; pa en analysis; e iew o he ASSB ma ke
1. In oduc ion
In ecen yea s, new ypes o ba e ies ha e been launched ha make use o li hium,
he ligh es elemen in he pe iodic able. Thei p ope ies di e in ela ion o size, shape,
ol age, and he eac ions employed. The li hium-ion ba e y ma ke is changing apidly,
wo h 34.2 billion USD in 2020, i is expec ed o ise o 182.53 billion USD in 2030, d i en by
an icipa ed g ow h in he elec ic ehicle (EV) ma ke [
1
]. Ad ancemen s in he de elop-
men o ma e ials and elec ode enginee ing ha e led o a educ ion in li hium-ion ba e y
cos s by 90% pe uni , and an inc ease in g a ime ic ene gy densi y om an ini ial le el
o ca 90 Wh kg
−1
o 250 Wh kg
−1
. A li hium-ion ba e y p o ides a high ol age window
o a ound 4 V, esul ing in g ea e olume ic and g a ime ic ene gy densi ies han o he
echa geable op ions, making i he echnology o choice o po able elec onics and powe
ools [
2
]. Wi h ega d o all-elec ic, plug-in and hyb id ehicles, he echnologies applied
in hem necessi a e he cons uc ion and use o echa geable li hium-ion ba e ies. An
al e na i e solu ion o a dual-ion ba e y exis s. Fab ica ed by ca ion in e cala ion, exam-
ples include an aluminum-g aphi e ba e y wi h high le els o e e sibili y and ene gy
densi y [
3
], and a calcium-ion ba e y capable o wo king s ably a oom empe a u e,
which has a no el cell con igu a ion wi h g aphi e as he ca hode and in oil as bo h he
anode and he cu en collec o [4].
Nume ous e iew pape s ha e been published on he cu en s a e-o - he-a o
LIBs [5,6]
, co e ing aspec s ela ed o sa e y conce ns [
7
] and ac o s a ec ing hei pe o -
mance a low empe a u e [8–10].
Ba e ies 2023,9, 157. h ps://doi.o g/10.3390/ba e ies9030157 h ps://www.mdpi.com/jou nal/ba e ies
Ba e ies 2023,9, 157 2 o 25
This wo k combines analysis o he majo echnical challenges aced in he de elop-
men o all-solid-s a e li hium-ion ba e ies wi h e alua ion o ela ed ad ancemen in
he global ma ke , based on pa en s, p o o ypes, and p oduc s p esen ed by companies,
esea ch cen e s and uni e si ies.
B ie his o y o LIBs
Resea ch on li hium-ion ba e ies (LIBs) began du ing he oil c isis in he 1970s, when
scien is s ponde ed op ions o al e na i e ene gy sou ces and he po en ial o echa geable
de ices. S anley Whi ingham, a chemis a Exxon mobile, de ised a no el ba e y design
wi h i anium disul ide as he ca hode and li hium me al as he anode, which could be
cha ged in a sho pe iod o ime (Figu e 1a). I was no success ul, howe e , due o he
he mal unaway e iden in ea ly es s. An enginee ing p o esso and physicis , John B.
Goodenough om he Uni e si y o Texas in Aus in, ad anced i by swapping ou he
i anium disul ide ca hode o li hium cobal oxide (LCO), he eby doubling he ene gy
capaci y o he ba e y (Figu e 1b) [
11
]. Fi e yea s la e , Aki a Yoshino om Meijo Uni-
e si y in Nagoya, Japan, applied a ca bonaceous ma e ial ins ead o he li hium me al
anode, which p o ed g ound-b eaking, as i was he i s p o o ype o a li hium-ion ba e y
wi hou li hium me al (Figu e 1c). Fo de eloping his “ echa geable echnology”, he h ee
a o emen ioned scien is s sha ed he Nobel P ize in 2019.
Ba e ies 2023, 9, 157 2 o 26
a oom empe a u e, which has a no el cell con igu a ion wi h g aphi e as he ca hode
and in oil as bo h he anode and he cu en collec o [4].
Nume ous e iew pape s ha e been published on he cu en s a e-o - he-a o LIBs
[5,6], co e ing aspec s ela ed o sa e y conce ns [7] and ac o s a ec ing hei
pe o mance a low empe a u e [8,9,10].
This wo k combines analysis o he majo echnical challenges aced in he
de elopmen o all-solid-s a e li hium-ion ba e ies wi h e alua ion o ela ed
ad ancemen in he global ma ke , based on pa en s, p o o ypes, and p oduc s p esen ed
by companies, esea ch cen e s and uni e si ies.
B ie his o y o LIBs
Resea ch on li hium-ion ba e ies (LIBs) began du ing he oil c isis in he 1970s, when
scien is s ponde ed op ions o al e na i e ene gy sou ces and he po en ial o
echa geable de ices. S anley Whi ingham, a chemis a Exxon mobile, de ised a no el
ba e y design wi h i anium disul ide as he ca hode and li hium me al as he anode,
which could be cha ged in a sho pe iod o ime (Figu e 1a). I was no success ul,
howe e , due o he he mal unaway e iden in ea ly es s. An enginee ing p o esso and
physicis , John B. Goodenough om he Uni e si y o Texas in Aus in, ad anced i by
swapping ou he i anium disul ide ca hode o li hium cobal oxide (LCO), he eby
doubling he ene gy capaci y o he ba e y (Figu e 1b) [11]. Fi e yea s la e , Aki a
Yoshino om Meijo Uni e si y in Nagoya, Japan, applied a ca bonaceous ma e ial ins ead
o he li hium me al anode, which p o ed g ound-b eaking, as i was he i s p o o ype
o a li hium-ion ba e y wi hou li hium me al (Figu e 1c). Fo de eloping his
“ echa geable echnology”, he h ee a o emen ioned scien is s sha ed he Nobel P ize in
2019.
Figu e 1. Ba e y designs by Whi ingham (a), Goodenough (b), and Yoshino (c).
In 1997, a esea ch eam led by Goodenough in oduced he ca hode ma e ial o
li hium i on phospha e (LFP), an al e na i e o LCO, since CO is high in oxici y and mo e
expensi e. LFP has he ad an ages o low ma e ial cos , non oxici y, a 3.5 V ope a ing
ol age (in con as wi h Li/Li+), a conside able heo e ical speci ic capaci y o 170 mAh
g-1, high s abili y, and p olonged cycle li e. Compa ed o o he ca hode ma e ials, hough,
he elec onic conduc i i y o he LPF ca hode is limi ed o 10
−9
o 10
−10
S cm
−1
[12,13]. O he
Figu e 1. Ba e y designs by Whi ingham (a), Goodenough (b), and Yoshino (c).
In 1997, a esea ch eam led by Goodenough in oduced he ca hode ma e ial o
li hium i on phospha e (LFP), an al e na i e o LCO, since CO is high in oxici y and mo e
expensi e. LFP has he ad an ages o low ma e ial cos , non oxici y, a 3.5 V ope a ing ol -
age (in con as wi h Li/Li+), a conside able heo e ical speci ic capaci y o
170 mAh g−1
,
high s abili y, and p olonged cycle li e. Compa ed o o he ca hode ma e ials, hough, he
elec onic conduc i i y o he LPF ca hode is limi ed o 10
−9
o 10
−10
S cm
−1
[
12
,
13
]. O he
d awbacks include a poo ion di usion a e, low ap densi y, and unaccep able elec ochem-
Ba e ies 2023,9, 157 3 o 25
ical pe o mance a low empe a u e, limi ing i s u he
de elopmen [14–16]
. A laye ed
ca hode ma e ial was p oposed la e , such as he combina ion o nickel, manganese, and
cobal (LiNi
1−x−y
Co
x
Mn
y
O
2
; e e ed o as he NMC ype o ca hode), which boas s high
speci ic capaci y, low in e nal esis ance, and heigh ened sa e y. Fo ms o NMC ca hode
wi h less cobal con en (e.g., NMC811, NMC442, NMC532) ha e ga ne ed a en ion as
cheape op ions, and a g ea deal o esea ch has been in es ed in de eloping cobal - ee
al e na i es. Compa ing wo designs capable o deli e ing 4.3 V, he g ea e amoun o
nickel in a ca hode such as NMC811 acili a es a highe speci ic capaci y o 200 mAh g
−1
han NMC532 (160 mAh g
−1
), e sus Li/Li+ con igu a ions. The inc eased le el o Ni
con en in he ca hode aises he eac i i y o he ca hode, howe e , due o he ins abili y
o he nickel ion wi h he liquid o ganic elec oly e, esul ing in wo- imes he ex en o
mois u e. This is why nickel- ich ca hode ma e ials need an addi ional elec ode coa ing o
p e en deg ada ion du ing ope a ion a high empe a u e [17,18].
Besides LIBs, a s ep-change in ene gy s o age is he appeal o echnologies ha di e
om Li-ion-based sys ems. Li hium-ai (Li-ai ) and li hium-sul u (Li-S) a e heo e ically
capable o p o iding he kind o he pe o mance equi ed o he u u e. Aqueous and non-
aqueous Li-ai ba e ies we e i s desc ibed in he li e a u e in [
19
] and [
20
,
21
] espec i ely.
The concep o elec ochemical ene gy con e sion and s o age, employing sul u as he
ca hode in an alkali me al anode ba e y da e back o a leas 1960 [
22
]. Reac ions a he
ca hode ( he posi i e elec ode) in Li-ai and Li-S cells in ol e he e e sible educ ion o
O
2
and S, espec i ely, and a e undamen ally di e en om hose in Li-ion cells. Al hough
heo e ically he ene gy densi ies o Li-ai and Li-S cells a e high (Table 1), nume ous issues
need o be add essed p io o shi ing he echnology om heo y o p ac ice [23].
Table 1. Theo e ical ene gy s o age o LIBs.
Ba e y Chemis y Cell
Po en ial/V
Theo e ical
Speci ic
Ene gy/Wh kg–1
Li-S2Li+S=Li2S 2.2 2567
Li-ai (non-aqueous) 2Li + O2= Li2O23.0 3505
Li-ai (aqueous) 2Li + 1
2O2+ H2O = 2LiOH 3.2 3582
Con empo a y Li-ion 0.5C6Li + Li0.5CoO2= 3C + LiCoO23.8 387
A shu le e ec epo ed o li hium polysul ide (LiPSs) and slow sul u eac ion
kine ics, caused by mul i-s ep phase ansi ions, se e ely limi he p ac ical applica ion
o
Li–S
ba e ies. These limi a ions can be o e come, hough, by adop ing a acile hy-
d o he mal me hod and pe o ming de ec enginee ing o syn hesize a cocklebu -like
sul u hos wi h a TiO
2
-VOx he e os uc u e (CTVHs) in he p oduc ion o long-li e Li–S
ba e ies [
24
]. He e os uc u es ha e he po en ial o aid he de elopmen o new Li–S
ba e ies o o he ene gy s o age sys ems, and could ind widesp ead applica ion in a ious
in e ace con ol solu ions.
1.1. Theo e ical Aspec s o Li-Ion Ba e y Technology
1.1.1. Key Pa ame e s o LIB De elopmen
Fo he la ge-scale applicabili y o LIBs, such as in EVs and a sma g id a angemen ,
i is necessa y o conside se e al ac o s. Pu ing LIBs in EVs, beyond ene gy- ela ed
conce ns, means add essing se e al ma e s including cos , cycle li e, sa e y, and en i on-
men al impac . In a sma g id se ing, he ela ed cos , sa e y, and li e cycle a e mo e
impo an han ene gy densi y [
25
]. Mode n LIBs a e limi ed o a g a ime ic ene gy den-
si y o
<250 Wh kg−1
and olume ic ene gy densi y o <650 Wh L
−1
; an inc ease in hese
is an icipa ed o up o ~500 Wh kg
−1
and
>
1000 Wh L
−1
, espec i ely. Such pe o mance
pa ame e s la gely depend on he p ope ies o he anode, ca hode and elec oly e ma e ials
employed in he ba e y sys em, he gi en en i onmen and in ended use.
Ba e ies 2023,9, 157 4 o 25
1.1.2. Solid Elec oly e In e ace (SEI) Fo ma ion
Cell eac ions ha pose a challenge o LIB echnology include he occu ence o a
solid elec oly e in e phase (SEI), elec oly e lammabili y, he dissolu ion o elec odes, and
dend i e g ow h [
26
]. The o ma ion o SEI in an ad anced echa geable ba e y sys em
a ises when such a ba e y is ope a ed beyond he he modynamic s abili y window o
he elec oly e [
27
]. The in e phase s ems om he sac i icial decomposi ion o elec oly ic
componen s, such as sol en , sal s, and addi i es, esul ing in he o ma ion o a hin ilm
which sepa a es he elec oly e om he elec ode [
28
]. I has been p o en ha he compo-
si ion o such an SEI is i al o supe io pe o mance o LIBs [
29
]. Ne e heless, li hium
ions a e consumed in he p esence o an excessi e SEI laye du ing deli hia ion, leading
o capaci y ade, a ise in impedance and c ea ion o a ba ie a he anode/elec oly e
in e ace [
30
–
33
]. Decomposi ion o o med SEI also ini ia es a chain o eac ions, and
u he esul s in he mal unaway o he LIB [30].
1.1.3. Sa e y Conce ns
Ano he c i ical conce n abou LIBs is ha o sa e y [
34
], and h ee main ca ego ies
exis : (1) he eac i i y o he ma e ial unde condi ions o abuse; (2) lammabili y o he
elec oly e; and (3) he oxici y o he subs ance i eleased in o he en i onmen h ough
a c ack in he cell package [
35
]. Reac ions inside he ba e y ha will esul in he mal
unaway o he sys em a e classi ied as anode–elec oly e, ca hode–elec oly e, and ca hode–
anode eac ions. Commonly used o ganic elec oly es ha e a a o able ope a ing ol age
window, ye unde ex eme condi ions o empe a u e and ol age hey may eac wi h
he elec odes and elease a signi ican amoun o hea and gas, e ec ing damage o o he
ma e ials o ailu e o he same inside he ba e y [
36
]. Anode–elec oly e eac ions a e
known o ini ia e a ise in hea p oduc ion, while ca hode-elec oly e and anode-ca hode
eac ions igge a combus ion p ocess; he la e only a ising when a conside able amoun
o hea is p oduced [
37
,
38
]. Such combus ibili y o a ca bona e elec oly e polyme in
ba e ies, leading o he mal unaway, is ins iga ed h ough mechanical o he mal s ess,
dend i e o ma ion, decomposi ion o he elec oly e, and cha ging issues ela ed o elec o-
chemical abuse [
39
]. Du ing abno mal cha ging condi ions, such as o e cha ging, li hium
is con inuously elimina ed on he ca hode side, inducing b eakdown o he ca hode and
oxygen e olu ion. Fu he e ec s comp ise oxida ion o o ganic sol en s in he sys em
and he in ense gene a ion o hea . Mo eo e , excessi e deposi ion o li hium a he anode
side ini ia es he o ma ion o dend i es, while he eac ion o such deposi ed li hium and
he ca bona e sol en p oduces a huge amoun o hea and gas. Ve y small lash poin s
a e associa ed wi h he decomposi ion o common li hium sal LiPF6 and he oxida ion
o ca bona e sol en s, e.g., e hylene ca bona e (EC), p opylene ca bona e (PC), dime hyl
ca bona e (DMC), e hyl me hyl ca bona e (EMC), die hyl ca bona e (DEC), and dime hyl
ca bona e (DME), which can be easily igge ed unde a s a e o high ol age o empe a u e.
Should he empe a u e o he ba e y sys em go up, he LiPF6 sal he mally decomposes
o PF5 be o e he sol en s decompose. This PF5 is a s ong Lewis acid highly eac i e
wi h o ganic sol en s, and such a eac ion could encou age he he mal decomposi ion
o ca bona e-based sol en s [
40
–
42
]. In addi ion, he unusual ise in empe a u e and
gene a ion o hea ini ia es side eac ions such as b eakdown o he SEI laye o des uc ion
o he sepa a o , which cons i u e causes o he mal unaway o he ba e y sys em [
43
–
45
].
In he case o EVs, a p ima y issue ela es o he size o he ba e y, namely a dec ease in
he a io be ween he he mal cooling a ea and hea gene a ed aises he isk o a i e in he
ba e y sys em [46,47].
Dend i e o ma ion ep esen s a majo issue in LIB echnology. Li me al has had eal
appeal as an anode ma e ial o LIBs due o i s ul ahigh speci ic capaci y o 3860 mAh g
−1
,
in addi ion o i s low nega i e edox po en ial o
−
3.04 V in compa ison wi h a s anda d
hyd ogen elec ode (SHE) [
48
]. The appea ance o li hium dend i e in Li me al ba e ies
is usually associa ed wi h abno mal ope a ion condi ions like o e cha ging o cha ging
in low empe a u es [
49
]. Typically, li hium dend i e g ow h occu s in he p esence o
Ba e ies 2023,9, 157 5 o 25
addi ional li hium ions ha accumula e o a e deposi ed on he anode su ace, ins ead o
being abso bed o inco po a ed in o he anode [
50
,
51
]. As a consequence, li hium ions
pe mea e he sepa a o , gi ing ise o sho ci cui s, sa e y issues, and ba e y ailu e. In
addi ion, li hium dend i es eac wi h he elec oly e, causing i o decompose h ough he
loss o li hium, he eby diminishing ba e y capaci y [52].
1.1.4. Ca hode Ma e ials Applicable in Li hium-Ion Ba e ies
Among he componen s in a Li-ion cell, i is he ca hodes ha es ic ene gy densi y
and dic a e he cos pe kilowa –hou . Mode n ca hode ma e ials a e ansi ion me al
oxides, and h ee classi ica ions o hem exis acco ding o hei c ys al s uc u e: (a) laye ed
LiMO
2
(M: Ti, V, C , Co, Ni), wi h a wo-dimensional laye ed c ys al s uc u e o LiCoO
2
;
(b) spinel oxides (e.g., LiMn
2
O
4
, LiTi
2
O
4
, LiNiO
2
) o h ee-dimensional mo phology; and
(c) he one-dimensional mo phology o polyanion oxides such as Li
2
(MoO
4
)
3
, Li
2
Fe
2
(WO
4
),
and LiFePO
4
. In such in e cala ion ca hode ma e ials, Li+ is he gues ion ha acili a es ion
di usion. Laye ed and spinel oxides ha e a close-packed s uc u e wi h high densi y, hence
hey possess su icien elec onic conduc i i y (10
−1
–10
−4
S cm
−1
). Al hough polyanion
oxides exhibi low densi y and poo elec onic conduc i i y, polyanion class ca hodes a o d
high he mal s abili y and g ea e sa e y han laye ed and spinel oxide ca hodes. Figu e 2
de ails he c ys al s uc u e o he ca hode ma e ials and hei ol age p o iles [53,54].
Ba e ies 2023, 9, 157 5 o 26
hyd ogen elec ode (SHE) [48]. The appea ance o li hium dend i e in Li me al ba e ies is
usually associa ed wi h abno mal ope a ion condi ions like o e cha ging o cha ging in
low empe a u es [49]. Typically, li hium dend i e g ow h occu s in he p esence o
addi ional li hium ions ha accumula e o a e deposi ed on he anode su ace, ins ead o
being abso bed o inco po a ed in o he anode [50,51]. As a consequence, li hium ions
pe mea e he sepa a o , gi ing ise o sho ci cui s, sa e y issues, and ba e y ailu e. In
addi ion, li hium dend i es eac wi h he elec oly e, causing i o decompose h ough he
loss o li hium, he eby diminishing ba e y capaci y [52].
1.1.4. Ca hode Ma e ials Applicable in Li hium-Ion Ba e ies
Among he componen s in a Li-ion cell, i is he ca hodes ha es ic ene gy densi y
and dic a e he cos pe kilowa –hou . Mode n ca hode ma e ials a e ansi ion me al
oxides, and h ee classi ica ions o hem exis acco ding o hei c ys al s uc u e: a)
laye ed LiMO
2
(M: Ti, V, C , Co, Ni), wi h a wo-dimensional laye ed c ys al s uc u e o
LiCoO
2
; b) spinel oxides (e.g., LiMn
2
O
4
, LiTi
2
O
4
, LiNiO
2
) o h ee-dimensional
mo phology; and c) he one-dimensional mo phology o polyanion oxides such as
Li
2
(MoO
4
)
3
, Li
2
Fe
2
(WO
4
), and LiFePO
4
. In such in e cala ion ca hode ma e ials, Li+ is he
gues ion ha acili a es ion di usion. Laye ed and spinel oxides ha e a close-packed
s uc u e wi h high densi y, hence hey possess su icien elec onic conduc i i y (10
−1–
10
−4
S cm
−1
). Al hough polyanion oxides exhibi low densi y and poo elec onic conduc i i y,
polyanion class ca hodes a o d high he mal s abili y and g ea e sa e y han laye ed and
spinel oxide ca hodes. Figu e 2 de ails he c ys al s uc u e o he ca hode ma e ials and hei
ol age p o iles [53,54].
Figu e 2. Discha ge p o iles (a) and c ys al s uc u es (b–d) o ep esen a i e in e cala ion ca hodes:
oli ine LiFePO
4
(b), laye ed LiCoO
2
(c) and spinel LiMn
2
O
4
(d).
Ou o he h ee classes o oxide ca hodes, laye ed oxides a e he p e e ed op ion.
LiNi
0.8
Co
15
Al
0.05
O
2
and LiNi
0.33
Co
0.33
Mn
0.33
O
2
demons a e he highes discha ge capaci y
(200 mAh g
−1
) and a e comme cially applied in Panasonic ba e ies o Tesla EVs.
Howe e , hese composi e ca hode ma e ials demons a e a e age discha ge ol age
dec eases du ing cycling. One way o o e coming his p oblem is o pe o m su ace
s abiliza ion, which minimizes olume changes, c acking, and su ace eac i i y [54]. I
ei he in ol es applying a su ace coa ing by chemical apo deposi ion and a omic laye
Figu e 2. Discha ge p o iles (a) and c ys al s uc u es (b–d) o ep esen a i e in e cala ion ca hodes:
oli ine LiFePO4(b), laye ed LiCoO2(c) and spinel LiMn2O4(d).
Ou o he h ee classes o oxide ca hodes, laye ed oxides a e he p e e ed op ion.
LiNi
0.8
Co
15
Al
0.05
O
2
and LiNi
0.33
Co
0.33
Mn
0.33
O
2
demons a e he highes discha ge capac-
i y (200 mAh g
−1
) and a e comme cially applied in Panasonic ba e ies o Tesla EVs. How-
e e , hese composi e ca hode ma e ials demons a e a e age discha ge ol age dec eases
du ing cycling. One way o o e coming his p oblem is o pe o m su ace s abiliza ion,
which minimizes olume changes, c acking, and su ace eac i i y [
54
]. I ei he in ol es

Ba e ies 2023,9, 157 6 o 25
applying a su ace coa ing by chemical apo deposi ion and a omic laye deposi ion
echniques [
55
], o adding inac i e dopan ca ions in o he laye ed oxide s uc u e. These
dopan s can subs i u e Li o ansi ion me al ca ions; o example, 1–5 mol. % o Mg
+2
ca ions lead o enhanced cycling s abili y. Ano he way pe ains o he design o g adien
and co e-shell ca hode pa icles. Co e-shell ma e ials a e usually syn hesized such ha he
uns able componen is in he co e and he he mally s able componen cons i u es he shell:
co e (Ni- ich o Li- ich) and shell (Mn- ich) [
56
]. Fo ins ance, he double-shelled ma e-
ial Li[Ni
0.8
Co
0.1
Mn
0.1
)
2/7
] co e [(Ni
1/3.
Co
1/3
Mn
1/3
)
3/14
] shell-1 [Ni
0.4
Co
0.2
Mn
0.4
)
1/2
O
2
)
shell-2 con ibu es o he cycling s abili y o he hyb id s uc u e, esul ing in supe io
elec ochemical pe o mance in compa ison wi h a homogeneous ca hode wi h he same
o e all composi ion [
57
]. Di e en enginee ing echniques ha e also been employed o
inc ease he elec ochemical pe o mance o a ca hode by emo ing he binde [
58
] and
a iously syn hesizing ca bon-based composi e ca hodes, e.g., by mixing in CNT and
g aphene oxide o by applying a coa ing o conduc ing polyme s, e.g., PANI [59,60].
1.1.5. Anode Ma e ials o Li hium-Ion Ba e ies
•Li hium-based anodes
In o de o achie e a high-ene gy densi y and as cha ge capabili y o LIBs, i is
necessa y o accele a e elec ochemical eac ions h ough cha ge ans e a he in e ace.
Rega dless o he ac ha Li me al as an anode ma e ial has a high heo e ical speci ic
capaci y (ca 3860 mAh g−1) and he mos nega i e po en ial (−3.040 V s. SHE), i su e s
om Li-dend i e o ma ion, poo in e acial con ac , no able olume changes and sensi i -
i y o he elec oly es [
61
]. Va ious me hods exis o egula e Li pla ing/s iping p ocesses,
esul ing in o ma ion o “dead Li”, i.e., a p o ec i e coa ing o he design o a composi e
li hium anode [
61
]. C ea ion o a composi e li hium anode equi es ha an addi ional com-
ponen is in oduced ha possesses a simila deli hia ion po en ial, and ce ain e e sible
s o age/ elease mechanisms o Li ions a e in place o acili a e he deli hia ion mechanism,
o example g aphene. The cycling pe o mance o a coin cell wi h a Li me al-g aphene
anode/LiFSI, DMC, HFE elec oly e/NCM523 ca hode main ains 210 cycles wi h a capaci y
e en ion o 80%, in compa ison wi h 110 cycles by a ba e Li anode [
62
]. In p ac ice, hough,
g aphi e o g aphene is widely applied as an anode ma e ial in li hium-ion ba e ies due o
he esul an a o able p ice-pe o mance a io [62].
•G aphene-based anodes
The use o g aphene as an anode in LIBs makes sense since g aphene can accele a e
elec onic ans e and educe con ac esis ance h ough good con ac be ween he ac i e
ma e ials and cu en collec o s, as well as he elec oly e, which educes pola iza ion.
G aphene ends o agglome a e, howe e , owing o
π
–
π
in e ac ion and an de Waal o ces
be ween laye s, po en ially hinde ing i s conduc i i y. Ne e heless, i is possible o ake
ad an age o his p ope y o g aphene and modi y i s s uc u e. In e ms o s uc u al o m,
g aphene is a ailable as a ma e ial in 1D ( ibe s), 2D ( ilm and pape ), and 3D (hyd ogel
o ms and honeycomb-like s uc u es). Applying such ma e ials as anodes gi es ise o
supe io a es (Table 2) [63].
•G aphi e-based anodes
G aphi e enables enhanced ull cell ene gy densi y h ough i s low deli hia ion po en-
ial (0.2 V s Li/Li+) and heo e ically high g a ime ic capaci y (372 mAh g−1) [64].
G aphi e pa icles a e cha ac e ized by a lake-like pa icle mo phology wi h wo
di e en su aces, basal and edge planes (Figu e 3) [
64
]. This 2D-laye ed s uc u e o
g aphi e causes he aniso opy o su ace ene gy and in luences elec onic, physicochemical
and mechanical p ope ies. Weak an de Waals o ces be ween he g aphi e laye s enable
he in e cala ion o ionic and molecula species ac oss he su aces. As a esul , expansion
a ec s he in e laye dis ance and e-s aking o he g aphi e laye s. A la ge in e laye
sepa a ion is a o able o elec ode ma e ials as i acili a es li hium-ion in e cala ion and
de-in e cala ion du ing cha ging and discha ging. This p ocess ends wi h he o ma ion o
Ba e ies 2023,9, 157 7 o 25
g aphi e in e cala ion compounds (GICs), ypically LiC6. GICs possess high eac i i y and
sensi i i y o oxygen and mois u e, esul ing in apid ma e ial deg ada ion.
Table 2. Pe o mance o LIBs wi h g aphene-based anode ma e ials.
Ma e ial Amoun o
G aphene Pe o mance
Li4Ti5/holey-g aphene 50 w .% 98 mAh cm3a 17.5 A g−1; 84% capaci y e en ion
a e 1000 cycles a 7 A g−1
Li4Ti5/g aphene 5 w .% 122 mAh cm3a 30◦C; 124.5 mA g−1; 98% capaci y
e en ion a e 300 cycles a 20◦C
G aphene-MnO2-GNRs 68 w .% 300 mAh cm3a 612 mAg−1a e 250 cycles a
0.4 A g−1
MoS2-g aphene 4.7 w .% 570 mAh cm3a 1A g−1; 894.1 mAh g−1a e
100 cycles a 0.1 A g−1
G aphene ancho ed wi h
Co3O424.6 w .%
484 mAh g−1a 0.5A g−1; 935 mAh g−1a e
30 cycles a 0.1 A g−1and a speci ic cu en o
0.05 Ag−1
Ba e ies 2023, 9, 157 7 o 26
G aphene-MnO
2
-
GNRs 68 w .% 300 mAh cm
3
a 612 mAg
−1
a e 250 cycles a 0.4 A
g
−1
MoS
2
-g aphene 4.7 w .% 570 mAh cm
3
a 1A g
−1
; 894.1 mAh g
−1
a e 100
cycles a 0.1 A g
−1
G aphene ancho ed
wi h Co
3
O
4
24.6 w .% 484 mAh g
−1
a 0.5A g
−1
; 935 mAh g
−1
a e 30 cycles
a 0.1 A g
−1
and a speci ic cu en o 0.05 Ag
−1
• G aphi e-based anodes
G aphi e enables enhanced ull cell ene gy densi y h ough i s low deli hia ion
po en ial (0.2 V s Li/Li+) and heo e ically high g a ime ic capaci y (372 mAh g
−1
) [64].
G aphi e pa icles a e cha ac e ized by a lake-like pa icle mo phology wi h wo
di e en su aces, basal and edge planes (Figu e 3) [64]. This 2D-laye ed s uc u e o
g aphi e causes he aniso opy o su ace ene gy and in luences elec onic,
physicochemical and mechanical p ope ies. Weak an de Waals o ces be ween he
g aphi e laye s enable he in e cala ion o ionic and molecula species ac oss he su aces.
As a esul , expansion a ec s he in e laye dis ance and e-s aking o he g aphi e laye s.
A la ge in e laye sepa a ion is a o able o elec ode ma e ials as i acili a es li hium-
ion in e cala ion and de-in e cala ion du ing cha ging and discha ging. This p ocess ends
wi h he o ma ion o g aphi e in e cala ion compounds (GICs), ypically LiC6. GICs
possess high eac i i y and sensi i i y o oxygen and mois u e, esul ing in apid ma e ial
deg ada ion.
Figu e 3. Schema ic illus a ion o he laye ed g aphi e s uc u e and he esul ing p esence o basal
and edge planes (a) showing he di e ence be ween zig-zag and a m chai su aces (b) and SEM
mic og aph o he basal and edge planes o a g aphi e pa icle (c).
• Ti-based oxides anode ma e ials
This ca ego y includes TiO
2
, Li
4
Ti
5
O
2
, Li
2
MTi
3
O
8
, MLi
2
Ti
6
O
14
and o he s, which
demons a e excellen in insic sa e y o hei high wo king po en ial (1.2–1.7 V s
Li+/Li), s able c ys al s uc u e du ing Li+ in e cala ion/de-in e cala ion, gene al
abundance and low cos , bu su e om poo elec onic conduc i i y (10
−13
S cm
−1
)
due o he highes alence s a e o Ti
+4
, hus es ic ing hei a e capabili ies [65,66].
The s uc u al s abili y, po e size and speci ic su ace a ea o Li2ZnTi3O8 (LZTO) co-
doped wi h Mo6+ and P5+ ions (LZM7TP3O) can be imp o ed by a one-s ep solid-s a e
echnique. When LZM7TP3O is used as he anode in a LiNi
0.5
Mn
1.5
O
4
/LZM
7
TP
3
O ull cell,
he discha ge speci ic capaci y o he ull cell eaches 214.3 mAh g
−1
a 0.5 C ac oss a
ol age ange o 2–4.55 V o he 1s cycle [67].
Figu e 3.
Schema ic illus a ion o he laye ed g aphi e s uc u e and he esul ing p esence o basal
and edge planes (
a
) showing he di e ence be ween zig-zag and a m chai su aces (
b
) and SEM
mic og aph o he basal and edge planes o a g aphi e pa icle (c).
•Ti-based oxides anode ma e ials
This ca ego y includes TiO
2
, Li
4
Ti
5
O
2
, Li
2
MTi
3
O
8
, MLi
2
Ti
6
O
14
and o he s, which
demons a e excellen in insic sa e y o hei high wo king po en ial (1.2–1.7 V s Li+/Li),
s able c ys al s uc u e du ing Li+ in e cala ion/de-in e cala ion, gene al abundance and
low cos , bu su e om poo elec onic conduc i i y (10
−13
S cm
−1
) due o he highes
alence s a e o Ti+4, hus es ic ing hei a e capabili ies [65,66].
Ba e ies 2023,9, 157 8 o 25
The s uc u al s abili y, po e size and speci ic su ace a ea o Li
2
ZnTi
3
O
8
(LZTO) co-
doped wi h Mo
6+
and P
5+
ions (LZM7TP3O) can be imp o ed by a one-s ep solid-s a e
echnique. When LZM7TP3O is used as he anode in a LiNi
0.5
Mn
1.5
O
4
/LZM
7
TP
3
O ull
cell, he discha ge speci ic capaci y o he ull cell eaches 214.3 mAh g
−1
a 0.5 C ac oss a
ol age ange o 2–4.55 V o he 1s cycle [67].
Li
4
Ti
5
O
2
is one is he mos widely s udied complex Ti-based oxides since i is easy
o ab ica e and boas s a s able ol age pla eau, sa e pe o mance and long cycling s abil-
i y; i ope a es in he po en ial window o 1.0–3.0 V, deli e ing a heo e ical capaci y o
175 mAh g−1[68].
The c ys al s uc u e o Li
4
Ti
5
O
2
possesses a spinel con igu a ion wi h an Fd3m space
g oup (Figu e 4). The 3D s uc u e o Li
4
Ti
5
O
2
secu es he p esence o he Li-ion anspo
pa hway, which in u n gua an ees a s able ol age pla eau du ing li hia ion, p e en ing
he o ma ion o li hium dend i es.
Ba e ies 2023, 9, 157 8 o 25
Figu e 4. C ys al s uc u es o Li4Ti5O2.
In o de o enhance he a e capabili y o Li4Ti5O2, i s composi es wi h ca bon-based
ma e ials ha e been ab ica ed by di e en me hods, o example by mixing in CNT o by
applying a coa ing o conduc ing polyme s, e.g., PANI [68,69].
• Silicon-based anode ma e ials
A he ou se , g aphi e-based anodes we e success ully adop ed o p e en dend i e
o ma ion du ing con inuous cha ge/discha ge cycles, and widely deployed in con en-
ional li hium-ion ba e ies. Howe e , his in e cala ion ype o anode ailed o p o ec he
ba e y om dend i e g ow h a as cha ging a es, while i also has a limi ed capaci y,
esul ing in poo ene gy densi y and es ic ing he ange o EVs. The in e cala ion speed
o li hium-ion in o a g aphi e s uc u e also in luences he powe o he gi en cells. G aph-
i e ha dly mee s he expec a ions o nex gene a ion li hium-ion ba e ies as a conse-
quence. Silicon was conside ed as a eplacemen o g aphi e anodes, as i boas ed much
g ea e li hium s o age (app ox. 4000 mAh g−1). Howe e , chemical bonds we e obse ed
o o m du ing li hium in e cala ion, gi ing ise o a new molecula s uc u e, in addi ion
o which he silicon expe ienced swelling and con ac ion du ing a con inuous cha ge-
discha ge cycle, leading o c acking and pul e iza ion. The SEI laye de o med nume ous
imes when cycling as a consequence, and he ela ed side eac ion consumed he li hium
in he ba e y, causing a loss in capaci y and inc ease in cell esis ance [70]. Thus, silicon-
based LIBs apidly lose ene gy s o age capabili y while cycling, and he high cos o silicon
limi s i s applicabili y in la ge-scale usage. Nume ous s a egies ha e been de eloped o
o e come hese de ec s, no ably applica ion o a ca bon coa ing, alloying and cons uc ion
o po ous s uc u es [71,72]. O he a ious syn he ic me hodologies o be esea ched, he
deposi ion o Si-me al alloys shows p omise as a p ac ical means o mass-p oducing po-
ous Si mic opa icles o he easons o simplici y and low cos [73]. A po ous Si anode
p epa ed by dealloying S -modi ied Al–Si alloys is expec ed o be mo e e ec i e a mi i-
ga ing expansion ia he in oduc ion o abundan nanopa icles [74]. Compa ed o g aph-
i e and silicon anode-based LIBs, li hium me al may s ill be he bes candida e o se e al
easons; al hough he associa ed d awback o dend i e o ma ion, which diminishes he
sa e y and se ice li e o a li hium me al-based LIB, is likely o es ic i s u iliza ion in
u u e high-ene gy de ices.
In addi ion o he anodes sui able o LIBs men ioned abo e, an alloying ype such
as aluminum anodes show po en ial since hey boas a high heo e ical capaci y (almos
1Ah g−1) [75]. Thei disad an age lies in cha ge anspo , as he olume ac ion o he
su ace oxide laye is signi ican smalle o aluminum pa icles (<10 μm), ha ing he e -
ec o se e ely blocking he anspo o elec ons. Mo eo e , he poo elec oly e we a-
bili y o he su ace oxide laye (a ising h ough he low a ini y o he sol en molecules
o he oxide laye ) educes cha ge anspo . G a ing pola amino g oups has been
demons a ed as an e ec i e means o imp o ing elec oly e we abili y [76].
1.2. Challenges Associa ed wi h All-Solid-S a e Ba e ies
Issues connec ed wi h LIB echnology in e ms o liquid elec oly es and g owing
demand o ene gy s o age de ices has p omp ed esea che s o seek ou al e na i e
Figu e 4. C ys al s uc u es o Li4Ti5O2.
In o de o enhance he a e capabili y o Li
4
Ti
5
O
2
, i s composi es wi h ca bon-based
ma e ials ha e been ab ica ed by di e en me hods, o example by mixing in CNT o by
applying a coa ing o conduc ing polyme s, e.g., PANI [68,69].
•Silicon-based anode ma e ials
A he ou se , g aphi e-based anodes we e success ully adop ed o p e en dend i e
o ma ion du ing con inuous cha ge/discha ge cycles, and widely deployed in con en-
ional li hium-ion ba e ies. Howe e , his in e cala ion ype o anode ailed o p o ec he
ba e y om dend i e g ow h a as cha ging a es, while i also has a limi ed capaci y,
esul ing in poo ene gy densi y and es ic ing he ange o EVs. The in e cala ion speed o
li hium-ion in o a g aphi e s uc u e also in luences he powe o he gi en cells. G aphi e
ha dly mee s he expec a ions o nex gene a ion li hium-ion ba e ies as a consequence.
Silicon was conside ed as a eplacemen o g aphi e anodes, as i boas ed much g ea e
li hium s o age (app ox. 4000 mAh g
−1
). Howe e , chemical bonds we e obse ed o o m
du ing li hium in e cala ion, gi ing ise o a new molecula s uc u e, in addi ion o which
he silicon expe ienced swelling and con ac ion du ing a con inuous cha ge-discha ge
cycle, leading o c acking and pul e iza ion. The SEI laye de o med nume ous imes
when cycling as a consequence, and he ela ed side eac ion consumed he li hium in he
ba e y, causing a loss in capaci y and inc ease in cell esis ance [
70
]. Thus, silicon-based
LIBs apidly lose ene gy s o age capabili y while cycling, and he high cos o silicon
limi s i s applicabili y in la ge-scale usage. Nume ous s a egies ha e been de eloped o
o e come hese de ec s, no ably applica ion o a ca bon coa ing, alloying and cons uc ion
o po ous s uc u es [
71
,
72
]. O he a ious syn he ic me hodologies o be esea ched, he
deposi ion o Si-me al alloys shows p omise as a p ac ical means o mass-p oducing po ous
Ba e ies 2023,9, 157 9 o 25
Si mic opa icles o he easons o simplici y and low cos [
73
]. A po ous Si anode p e-
pa ed by dealloying S -modi ied Al–Si alloys is expec ed o be mo e e ec i e a mi iga ing
expansion ia he in oduc ion o abundan nanopa icles [
74
]. Compa ed o g aphi e
and silicon anode-based LIBs, li hium me al may s ill be he bes candida e o se e al
easons; al hough he associa ed d awback o dend i e o ma ion, which diminishes he
sa e y and se ice li e o a li hium me al-based LIB, is likely o es ic i s u iliza ion in
u u e high-ene gy de ices.
In addi ion o he anodes sui able o LIBs men ioned abo e, an alloying ype such
as aluminum anodes show po en ial since hey boas a high heo e ical capaci y (almos
1Ah g
−1
) [
75
]. Thei disad an age lies in cha ge anspo , as he olume ac ion o he
su ace oxide laye is signi ican smalle o aluminum pa icles (<10
µ
m), ha ing he e ec
o se e ely blocking he anspo o elec ons. Mo eo e , he poo elec oly e we abili y o
he su ace oxide laye (a ising h ough he low a ini y o he sol en molecules o he
oxide laye ) educes cha ge anspo . G a ing pola amino g oups has been demons a ed
as an e ec i e means o imp o ing elec oly e we abili y [76].
1.2. Challenges Associa ed wi h All-Solid-S a e Ba e ies
Issues connec ed wi h LIB echnology in e ms o liquid elec oly es and g owing de-
mand o ene gy s o age de ices has p omp ed esea che s o seek ou al e na i e solu ions,
ushe ing in he e a o solid-s a e elec oly es (SSEs) and all-solid-s a e ba e ies (ASSBs).
SSEs a e conside ed one o he bes app oaches o sol ing he li hium dend i e o ma ion
in ba e ies. Replacing ola ile, lammable liquid elec oly es wi h SSEs e ec i ely c ea es
an impene able solid ba ie o li hium dend i es, allowing he use o a me al li hium
anode [
77
–
79
]. In an ideal si ua ion, he edox o Li-ion is he only eac ion o occu a
he anode side, and he li hium s ipping and pla ing a e supposed o be homogeneous in
ASSBs. I has p o en di icul o ab ica e such supe io ASSBs, hough. This is due o he
p esence o side in e acial eac ions ha cause ins abili y and he o ma ion o dend i es a
he in e ace o he li hium me al anode, as well as low ionic conduc i i y and poo physical
con ac a he ca hode in e ace. This subsequen ly leads o in e acial deg ada ion, poo
cyclic s abili y, educed ope a ing speed, and space cha ge o ma ion laye s, among o he
issues [80].
In e acial issues ha pose challenges in he manu ac u e and scaling up o ASSBs
mainly a ise om he ins abili y o SSE. The chemical po en ial o he highes occupied
molecula o bi al (HOMO) and lowes unoccupied molecula o bi al (LUMO) o he elec-
oly e de e mines he s abili y o he elec oly e. Thus, an in e ace is he modynamically
s able i he chemical po en ial o anode and ca hode ma e ials is si ua ed be ween he
LUMO and HOMO. O he wise, an in e laye can appea a bo h he anode and ca hode
in e ace i he chemical po en ial o he Li me al anode exceeds ha o he LUMO. and
chemical po en ial o ca hode is less han o he HOMO [
81
]. Th ee ypes o ASSB in e ace
exis : (a) he modynamically s able (no chemical eac ions); (b) non-passi a ed mixed-
conduc i e in e phase; and (c) passi a ed kine ically s able in e phase, c ea ed by chemical
eac ions a he in e ace o he elec oly e and elec ode [
82
,
83
]. The mixed-conduc i e
in e phase shows high elec onic and ionic conduc i i y, hence decomposi ion o he elec-
oly e a his in e phase is spon aneous and p omo es educ ion in he elec oly e [
84
,
85
].
Howe e , e en in he kine ically s able in e phase, educ ion in SSE is spon aneous. Ne -
e heless, he in e phase is elec onically insula ed and he elec onic ba ie po en ial
dec eases ac oss he in e phase [
86
,
87
]. The chemical eac ion a his in e ace esul s in a
s able solid elec oly e in e ace wi h diminished elec onic conduc i i y, u he limi ing
he possibili y o addi ional side eac ions. The o ma ion o he modynamically and kine -
ically s able in e aces could p o e bene icial o he long- e m pe o mance o he ba e y.
Howe e , he majo i y o he epo ed solid elec oly es a e he modynamically uns able
as ega ds he li hium me al anode, and a kine ically s able, mixed-conduc i e in e ace is
o en obse ed on he anode side o he solid elec oly e [88,89].
Ba e ies 2023,9, 157 16 o 25
2.3. O e iew o Hyb id (Ce amic/Polyme ) Solid Elec oly es
To imp o e he pe o mance o solid elec oly es, scien is s p opose in e cala ion o a
polyme ma e ial wi h ce amic componen s o c ea e a hyb id polyme /ce amic elec oly e.
As his cons i u es a ela i ely ecen ad ancemen , e y ew pa en s appea ed on he
subjec in he i s hal o in es iga ed pe iod (2000–2010) (Figu e 10), bu mo e ha e been
published since. I is no able ha a e 2017 in e es in hyb id solid elec oly es echnologies
inc eased exponen ially, eaching nin h posi ion in ela ion o pa en s egis e ed in 2020.
Ba e ies 2023, 9, 157 15 o 25
Figu e 9. Compa ison o dis ibu ion o pa en s on he opics o polyme /solid elec oly es and PEO
solid elec oly es in 2010 (a) and 2020 (b).
2.3. O e iew o Hyb id (Ce amic/Polyme ) Solid Elec oly es
To imp o e he pe o mance o solid elec oly es, scien is s p opose in e cala ion o
a polyme ma e ial wi h ce amic componen s o c ea e a hyb id polyme /ce amic elec o-
ly e. As his cons i u es a ela i ely ecen ad ancemen , e y ew pa en s appea ed on
he subjec in he i s hal o in es iga ed pe iod (2000–2010) (Figu e 10), bu mo e ha e
been published since. I is no able ha a e 2017 in e es in hyb id solid elec oly es ech-
nologies inc eased exponen ially, eaching nin h posi ion in ela ion o pa en s egis e ed
in 2020.
Figu e 10. P og ession o pa en applica ions on hyb id (ino ganic-polyme ic)/solid elec oly es in
2000–2020.
This e iew disclosed a me hod o ab ica ing an ion-doped, all-solid-s a e li hium-
ion conduc i e ma e ial wi h li hium ionic conduc i i y, which included a con inuous
Taylo low eac o , and syn hesis o a LaZ Ga(OH)x me al hyd oxide p ecu so by co-
p ecipi a ion; he p oduc ion o ee-s anding, double-laye ed o iple-laye ed o ganic-
ino ganic hyb id solid elec oly e memb anes is also desc ibed, acili a ed by applying he
all-solid-s a e li hium-ion conduc i e ma e ial o a polyme ma e ial and coa ing i ia a
blade coa ing me hod [132]. Ano he pa en published in 2021 de ails a composi e solid
elec oly e sepa a ion memb ane ha employs an ino ganic ibe and a seconda y ba e y
wi h he same ibe , a composi e solid elec oly e sepa a ion memb ane including he in-
o ganic ibe , a sodium oxide-based ce amic ma e ial imp egna ed in he ino ganic ibe ,
and an elec oly e inco po a ed in he ino ganic ibe , in o which he sodium oxide-based
ce amic ma e ial is imp egna ed [133]. An in en ion is epo ed o an all-solid-s a e sec-
onda y li hium ba e y ep esen ing a combina ion o a sul ide-based solid elec oly e po-
si ioned on he posi i e elec ode wi h an oxide-based solid elec oly e and a second binde ,
Figu e 10.
P og ession o pa en applica ions on hyb id (ino ganic-polyme ic)/solid elec oly es in
2000–2020.
This e iew disclosed a me hod o ab ica ing an ion-doped, all-solid-s a e li hium-
ion conduc i e ma e ial wi h li hium ionic conduc i i y, which included a con inuous
Taylo low eac o , and syn hesis o a LaZ Ga(OH)x me al hyd oxide p ecu so by co-
p ecipi a ion; he p oduc ion o ee-s anding, double-laye ed o iple-laye ed o ganic-
ino ganic hyb id solid elec oly e memb anes is also desc ibed, acili a ed by applying he
all-solid-s a e li hium-ion conduc i e ma e ial o a polyme ma e ial and coa ing i ia a
blade coa ing me hod [
132
]. Ano he pa en published in 2021 de ails a composi e solid elec-
oly e sepa a ion memb ane ha employs an ino ganic ibe and a seconda y ba e y wi h
he same ibe , a composi e solid elec oly e sepa a ion memb ane including he ino ganic
ibe , a sodium oxide-based ce amic ma e ial imp egna ed in he ino ganic ibe , and an
elec oly e inco po a ed in he ino ganic ibe , in o which he sodium oxide-based ce amic
ma e ial is imp egna ed [
133
]. An in en ion is epo ed o an all-solid-s a e seconda y
li hium ba e y ep esen ing a combina ion o a sul ide-based solid elec oly e posi ioned
on he posi i e elec ode wi h an oxide-based solid elec oly e and a second binde , as well
as a nega i e elec ode posi ioned on he solid elec oly e laye inco po a ing a nega i e
elec ode ac i e ma e ial [
134
]. Pa en s discou se on ends in echnological de elopmen
ha could become global p oduc s. They usually e lec he ma ke pene a ion po en ial
o a echnology, and aid o ecas o he de elopmen o a pa icula echnological a ea.
In o de o help comp ehend and analyze he e ec i eness o pa en echnologies in he
ma ke , a sepa a e s udy o ASSBs companies was conduc ed, as p esen ed below.
3. Global O e iew o ASSB-P oducing Solid-S a e Ba e y Companies
Global demand o ASSBs has g own s eadily in ecen yea s due o he ac ha solid-
s a e ba e ies a e becoming mo e eadily applied by he au omo i e, indus ial, consume ,
and po able elec onics indus ies. Solid-s a e ba e ies a e sa e , mo e en i onmen ally
iendly, and ha e a highe ene gy densi y and longe se ice li e han li hium-ion ba e ies

Ba e ies 2023,9, 157 17 o 25
wi h a liquid elec oly e. This makes hem an economical and sensible choice in he ba e y
ma ke wo ldwide. Se e al in e na ional companies ha e ocused on de eloping and
p oducing solid-s a e ba e ies.
A he o e on o inno a ion in semi solid-s a e ba e ies a e de elope s o solid-
s a e ba e ies o he EV sec o , companies, uni e si ies, and go e nmen agencies. This
sec ion p o ides an o e iew o companies a he helm o he global solid-s a e ba e y
ma ke . Based on in o ma ion ga he ed om websi es, news a icles, ma ke ing epo s,
and scien i ic jou nals, a lis o such majo playe s was compiled.
Keywo ds we e iden i ied in he Google Ads and Google T ends sea ch ools o
de ine ele an sea ch pa ame e s, as ollows: “solid-s a e elec oly e” (SSE), “all-solid-s a e
ba e y” (ASSB), “solid-s a e ba e y” (SSB), and “solid-s a e li hium-ion ba e y”. Using
hese keywo ds, leading coun ies we e iden i ied in e ms o he numbe o eques s
o da a o he cu en yea in he Google T ends web app. Then an o e iew o which
coun ies we e ac i ely in ol ed in ASSB de elopmen was o med based upon each
keywo d. Google sea ches we e subsequen ly ca ied ou , whe e a que y was en e ed o
each key wo d and coun y om he compiled lis , in o de o ob ain maximal access o
cu en da a on en i ies pa icipa ing in ASSB ac i i ies. In acco dance wi h co po a e web
pages, publica ions on he opic, ma ke ing and scien i ic epo s, and media discussions, a
ull lis o 93 companies and ins i u ions was d awn up wi h ele ance o he c ea ion and
de elopmen global ASSB ma ke .
The analysis iden i ied 93 companies om a ious coun ies, led by he USA, Japan,
China, Ge many, F ance, Canada, he UK, and Sou h Ko ea (Figu e 11)
Ba e ies 2023, 9, 157 16 o 25
as well as a nega i e elec ode posi ioned on he solid elec oly e laye inco po a ing a neg-
a i e elec ode ac i e ma e ial [134]. Pa en s discou se on ends in echnological de elop-
men ha could become global p oduc s. They usually e lec he ma ke pene a ion po en-
ial o a echnology, and aid o ecas o he de elopmen o a pa icula echnological a ea.
In o de o help comp ehend and analyze he e ec i eness o pa en echnologies in he
ma ke , a sepa a e s udy o ASSBs companies was conduc ed, as p esen ed below.
3. Global O e iew o ASSB-P oducing Solid-S a e Ba e y Companies
Global demand o ASSBs has g own s eadily in ecen yea s due o he ac ha
solid-s a e ba e ies a e becoming mo e eadily applied by he au omo i e, indus ial, con-
sume , and po able elec onics indus ies. Solid-s a e ba e ies a e sa e , mo e en i on-
men ally iendly, and ha e a highe ene gy densi y and longe se ice li e han li hium-
ion ba e ies wi h a liquid elec oly e. This makes hem an economical and sensible choice
in he ba e y ma ke wo ldwide. Se e al in e na ional companies ha e ocused on de el-
oping and p oducing solid-s a e ba e ies.
A he o e on o inno a ion in semi solid-s a e ba e ies a e de elope s o solid-
s a e ba e ies o he EV sec o , companies, uni e si ies, and go e nmen agencies. This
sec ion p o ides an o e iew o companies a he helm o he global solid-s a e ba e y
ma ke . Based on in o ma ion ga he ed om websi es, news a icles, ma ke ing epo s,
and scien i ic jou nals, a lis o such majo playe s was compiled.
Keywo ds we e iden i ied in he Google Ads and Google T ends sea ch ools o de-
ine ele an sea ch pa ame e s, as ollows: “solid-s a e elec oly e” (SSE), “all-solid-s a e
ba e y” (ASSB), “solid-s a e ba e y” (SSB), and “solid-s a e li hium-ion ba e y”. Using
hese keywo ds, leading coun ies we e iden i ied in e ms o he numbe o eques s o
da a o he cu en yea in he Google T ends web app. Then an o e iew o which coun-
ies we e ac i ely in ol ed in ASSB de elopmen was o med based upon each keywo d.
Google sea ches we e subsequen ly ca ied ou , whe e a que y was en e ed o each key
wo d and coun y om he compiled lis , in o de o ob ain maximal access o cu en
da a on en i ies pa icipa ing in ASSB ac i i ies. In acco dance wi h co po a e web pages,
publica ions on he opic, ma ke ing and scien i ic epo s, and media discussions, a ull
lis o 93 companies and ins i u ions was d awn up wi h ele ance o he c ea ion and
de elopmen global ASSB ma ke .
The analysis iden i ied 93 companies om a ious coun ies, led by he USA, Japan,
China, Ge many, F ance, Canada, he UK, and Sou h Ko ea (Figu e 11)
Figu e 11. Classi ica ion based on geog aphical posi ion o companies pa icipa ing in ASSB ac i i-
ies.
Figu e 11.
Classi ica ion based on geog aphical posi ion o companies pa icipa ing in ASSB ac i i ies.
Du ing he nex s age o he analysis, da a on he ope a ions o he i ms, hei esea ch
e o s, and he compliance o such echnologies wi h he ASSB concep we e s udied in de-
ail. Based on he indings, en i ies we e classi ied acco ding o he ollowing
eigh c i e ia
:
1. Companies no p o iding de ailed in o ma ion on ASSBs
2. Supplie s and manu ac u e s o ma e ials and componen s o ASSBs
3. Companies applying hyb id echnologies
4.
Companies coope a ing wi h o he i ms and in es ing in he de elopmen o ASSBs
5. Companies wi h hei own echnology ha lack a p o o ype o de ice
Ba e ies 2023,9, 157 18 o 25
6.
Companies conduc ing esea ch on he opic ha ha e no openly disclosed
any esul s
7. Companies ha ha e published in o ma ion on ASSB p o o ypes
8. Companies wi h an ASSB p oduc sold comme cially
In acco dance wi h he abo e c i e ia, 36 companies wi h ASBB p o o ypes and de ices
we e selec ed. These companies we e p ima ily loca ed in de eloped coun ies, i.e., he
USA, Japan, China, F ance, Canada, and G ea B i ain (Figu e 12). The au omo i e sec o
p o ides mos o he impe us o SSB de elopmen , and his is expec ed o be he main
applica ion o SSBs in he medium and long e m. Widesp ead adop ion o oxide and
sul ide-based SSBs by au omo i e i ms, howe e , is no an icipa ed o ano he i e yea s.
Un il ha ime, he eme ging ma ke o ino ganic SSBs appea s o be o consume goods
(e.g., lap ops, sma phones, and powe ools), as equi emen s and es ing p ocedu es
may be less s ingen . Vehicle manu ac u e s a e likely o be he p ima y ini ial use s
o oxide SSBs, possibly in pa allel wi h p oduce s o indus ial hea y-du y machine y
and equipmen o ha sh en i onmen s, as such ba e ies migh p o e su icien ly obus .
The expense associa ed wi h he new echnology means ha high-end sec o s will a ge
SSBs i s . Once economies o scale b ing abou cos educ ions, SSBs could become mo e
appealing o u he applica ions, such as uck and s a iona y s o age uni s. A e 2035,
SSBs migh e en ind hei way in o o he a eas such as passenge a ia ion. [135]
Ba e ies 2023, 9, 157 17 o 25
Du ing he nex s age o he analysis, da a on he ope a ions o he i ms, hei e-
sea ch e o s, and he compliance o such echnologies wi h he ASSB concep we e s ud-
ied in de ail. Based on he indings, en i ies we e classi ied acco ding o he ollowing
eigh c i e ia:
1. Companies no p o iding de ailed in o ma ion on ASSBs
2. Supplie s and manu ac u e s o ma e ials and componen s o ASSBs
3. Companies applying hyb id echnologies
4. Companies coope a ing wi h o he i ms and in es ing in he de elopmen o ASSBs
5. Companies wi h hei own echnology ha lack a p o o ype o de ice
6. Companies conduc ing esea ch on he opic ha ha e no openly disclosed any esul s
7. Companies ha ha e published in o ma ion on ASSB p o o ypes
8. Companies wi h an ASSB p oduc sold comme cially
In acco dance wi h he abo e c i e ia, 36 companies wi h ASBB p o o ypes and de-
ices we e selec ed. These companies we e p ima ily loca ed in de eloped coun ies, i.e.,
he USA, Japan, China, F ance, Canada, and G ea B i ain (Figu e 12). The au omo i e
sec o p o ides mos o he impe us o SSB de elopmen , and his is expec ed o be he
main applica ion o SSBs in he medium and long e m. Widesp ead adop ion o oxide
and sul ide-based SSBs by au omo i e i ms, howe e , is no an icipa ed o ano he i e
yea s. Un il ha ime, he eme ging ma ke o ino ganic SSBs appea s o be o consume
goods (e.g., lap ops, sma phones, and powe ools), as equi emen s and es ing p oce-
du es may be less s ingen . Vehicle manu ac u e s a e likely o be he p ima y ini ial us-
e s o oxide SSBs, possibly in pa allel wi h p oduce s o indus ial hea y-du y machine y
and equipmen o ha sh en i onmen s, as such ba e ies migh p o e su icien ly obus .
The expense associa ed wi h he new echnology means ha high-end sec o s will a ge
SSBs i s . Once economies o scale b ing abou cos educ ions, SSBs could become mo e
appealing o u he applica ions, such as uck and s a iona y s o age uni s. A e 2035,
SSBs migh e en ind hei way in o o he a eas such as passenge a ia ion. [135]
Figu e 12. Pie cha o companies ha claim o ha e an ASSB p o o ype o de ice based on hei
geog aphical posi ion.
Va ious po en ial business applica ions exis o ASSBs, as can be seen om he Table
4.
Table 4. Indus ial sec o s applicable o ASSB echnology.
Ac i i y
De ices
Figu e 12.
Pie cha o companies ha claim o ha e an ASSB p o o ype o de ice based on hei
geog aphical posi ion.
Va ious po en ial business applica ions exis o ASSBs, as can be seen om he Table 4.
The mos impo an applica ions o ASSBs a e elec ic ehicles, consume elec onics,
and s a iona y ene gy s o age uni s (Figu e 13). I is expec ed ha mo e emphasis will
be placed on he la e wi h he aim o ensu ing ene gy independence in Eu ope in he
coming yea s.
The composi ions o ma e ials employed in he ab ica ion o solid-s a e elec oly es
a e illus a ed in Figu e 14. Ino ganic ma e ials we e ound in almos wo- hi ds o he
companies analyzed. Acco ding o he ASSB oadmap p epa ed by F aunho e , he sha e o
ASSBs in he global demand o LIB is cu en ly less han 0.5%. Fo he sake o compa ison,
he global ba e y ma ke is domina ed by lead acid ba e ies and LIBs.
Ba e ies 2023,9, 157 19 o 25
Table 4. Indus ial sec o s applicable o ASSB echnology.
Ac i i y De ices
EVs, HEVs, EVs wi h wo-wheel ba e y swapping unc ionali y, elec ic bicycles, hyb id ehicles
Consume elec onics
Au onomous senso de ices, sma homes (HVAC, secu i y sys ems, ligh s); au omo i e
(in o ainmen sys ems, senso s); logis ics (asse acking); wea ables dedica ed o he needs o nex
gene a ion IoT edge nodes; minia u e de ices; elec onics; s andby powe supplies; po able de ices,
he In e ne o Things; eme gency powe p o ec ion; wa ches; au onomous senso s; Real Time Clock
(RTC); p oduc s wi h semiconduc o s; au omo i e elec ical equipmen ; sa e y UPS sys ems
Medicine/Heal h Medical de ices (biome ic moni o ing); medical implan s; heal h and i ness applica ions; o he
medical applica ions
Ae ospace Sa elli es
Indus ial
Fac o y/in as uc u e/indus ial equipmen ; u al elec i ica ion; hyb id powe uni s o indus ies
manu ac u ing, and p oduc ion; 3C consump ion indus ies; pa ol inspec ion secu i y sys ems;
ae ial pho og aphy and ela ed indus ies; obo ics and AI; IoT de ices
S a iona y ene gy s o age In eg a ion o enewables; ene gy & u ili ies; localized powe sou ces; powe b idging; g id s o age;
la ge-scale ene gy s o age
Mili a y A ia ion; ma ine; de ense
Ba e ies 2023, 9, 157 18 o 25
EVs, HEVs, EVs wi h wo-wheel ba e y swapping unc ionali y, elec-
ic bicycles, hyb id ehicles
Consume elec-
onics
Au onomous senso de ices, sma homes (HVAC, secu i y sys ems,
ligh s); au omo i e (in o ainmen sys ems, senso s); logis ics (asse
acking); wea ables dedica ed o he needs o nex
gene a ion IoT edge
nodes; minia u e de ices; elec onics; s andby powe supplies; po able
de ices, he In e ne o
Things; eme gency powe p o ec ion; wa ches;
au onomous senso s; Real Time Clock (RTC); p oduc s wi h semicon-
duc o s; au omo i e elec ical equipmen ; sa e y UPS sys ems
Medicine/Heal h
Medical de ices (biome ic moni o ing); medical implan s; heal h and
i ness applica ions; o he medical applica ions
Ae ospace
Sa elli es
Indus ial
Fac o y/in as uc u e/indus ial equipmen ; u al elec i ica ion; hy-
b id powe uni s o indus ies manu ac u ing, and p oduc ion; 3C
consump ion
indus ies; pa ol inspec ion secu i y sys ems; ae ial pho-
og aphy and ela ed indus ies; obo ics and AI; IoT de ices
S a iona y en-
e gy s o age
In eg a ion o enewables; ene gy & u ili ies; localized powe sou ces;
powe b idging; g id s o age; la ge-scale ene gy s o age
Mili a y
A ia ion; ma ine; de ense
The mos impo an applica ions o ASSBs a e elec ic ehicles, consume elec on-
ics, and s a iona y ene gy s o age uni s (Figu e 13). I is expec ed ha mo e emphasis will
be placed on he la e wi h he aim o ensu ing ene gy independence in Eu ope in he
coming yea s.
Figu e 13. Sec o s applicable o ASSB use.
The composi ions o ma e ials employed in he ab ica ion o solid-s a e elec oly es
a e illus a ed in Figu e 14. Ino ganic ma e ials we e ound in almos wo- hi ds o he
companies analyzed. Acco ding o he ASSB oadmap p epa ed by F aunho e , he sha e
o ASSBs in he global demand o LIB is cu en ly less han 0.5%. Fo he sake o compa -
ison, he global ba e y ma ke is domina ed by lead acid ba e ies and LIBs.
E en hough ASSBs a e a a ela i ely ea ly s age o de elopmen and i is di icul
o p edic he u u e ma ke , he au ho s ha e a emp ed o make o ecas s. In ela ion o
he solid elec oly e (SE), he key componen o an ASSB, h ee ma e ial g oups s and ou
as p omising candida es-oxide, sul ide, and polyme elec oly es. A he momen , he only
solid-s a e ba e ies gene ally a ailable a e polyme ASSBs ha ea u e in ce ain buses.
The cu en global p oduc ion capaci y o ASSB is es ima ed o be below 2 GWh, and
almos exclusi ely based on polyme ASSB echnology. The F aunho e epo s a es ha
Figu e 13. Sec o s applicable o ASSB use.
Ba e ies 2023, 9, 157 19 o 25
pilo p oduc ion o polyme -based ASSBs and he ini ial manu ac u e o SSB cells wi h Si
anodes and sul ide SE a e planned o commence in ca 2025. ASSB pilo p oduc ion wi h
Li me al anodes and oxide SE is expec ed o s a om 2025 and he sul ide SE-based SSB
hen 2028.
F om an expe anking, he mos p omising concep s include P oLogium, Quan um
Scape P oLogium (NMC + Gel o Gel + Oxide elec oly e), Solid Powe , Samsung-R&D
(NMC + sulphide), and Blue Solu ions–Bollo e, Hyd o Quebec (LFP + polyme elec o-
ly e). The a ious company announcemen s a e summa ized in he Tables con ained in
he supplemen a y da a [135].
Figu e 14. Classi ica ion o ASSBs based on he ma e ial used in he ab ica ion o SSE.
The analysis o companies is complica ed by he ac ha in an e o o gain a com-
pe i i e ad an age in he global ma ke , many en i ies ha e elec ed o coope a ion, lead-
ing o a me ge o companies o he c ea ion o sepa a e di isions o he esea ch and
de elopmen o solid-s a e ba e ies.
I should be also no ed ha open da a on p oduc s a e limi ed, and echnical desc ip-
ions o en lack in o ma ion, hinde ing he de elopmen o coope a ion be ween compa-
nies and esea ch cen e s.
4. Conclusions, Rema ks and Fu u e Pe spec i es
The ansi ion o clean ene gy equi es he in oduc ion o ene gy s o age de ices
wi h excellen elec ochemical p ope ies ha espec economic, en i onmen al, and so-
cial aspec s. Analysis o issues associa ed wi h liquid elec oly es led scien is s in he pas
o conside solid-s a e elec oly es, which made i possible o apply a me al li hium anode
and design all solid-s a e ba e ies. ASSB echnology is now a leading con ende wi h e-
spec o ene gy densi y and sa e y.
The pu pose o his e iew a icle was o analyze he p esence o ASSBs in he global
ma ke h ough he e olu ion o pa en s, p o o ypes and de ices p esen ed by companies,
esea ch cen e s, and uni e si ies.
Resea ch on pa en s egis e ed in he pas wo decades showed ha e e ences in
hem o ASSBs saw an exponen ial inc ease by 2021. Mos o he pa en s ela ed o solid-
s a e elec oly es, such as solid ino ganic elec oly es, whe e o emos (in e ms o he
numbe o pa en s issued las yea ) a e sul ide, ga ne and pe o ski e ypes: 196, 42, and
16 espec i ely. The second mos popula we e solid polyme elec oly es (SPEs), wi h
o e 60 pa en s, while solid hyb id elec oly es (SHEs) appea ed in only 12 pa en s.
A lis o 93 ASSB-associa ed companies om a ound he wo ld is p o ided, based on
in o ma ion a ailable on company websi es, social media pla o ms, and in epo s and
academic publica ions. I should be no ed ha despi e he ela i ely high numbe o man-
u ac u ing companies, mos o hem do no p o ide echnological in o ma ion o pe mi
e alua ion o he composi ion and e ec i eness o hei ene gy s o age de ices. Gi en his
ac , o de ailed analysis, we selec ed 35 companies ha p o ided su icien da a on ASSB
Figu e 14. Classi ica ion o ASSBs based on he ma e ial used in he ab ica ion o SSE.
Ba e ies 2023,9, 157 20 o 25
E en hough ASSBs a e a a ela i ely ea ly s age o de elopmen and i is di icul o
p edic he u u e ma ke , he au ho s ha e a emp ed o make o ecas s. In ela ion o he
solid elec oly e (SE), he key componen o an ASSB, h ee ma e ial g oups s and ou as
p omising candida es-oxide, sul ide, and polyme elec oly es. A he momen , he only
solid-s a e ba e ies gene ally a ailable a e polyme ASSBs ha ea u e in ce ain buses.
The cu en global p oduc ion capaci y o ASSB is es ima ed o be below 2 GWh, and
almos exclusi ely based on polyme ASSB echnology. The F aunho e epo s a es ha
pilo p oduc ion o polyme -based ASSBs and he ini ial manu ac u e o SSB cells wi h Si
anodes and sul ide SE a e planned o commence in ca 2025. ASSB pilo p oduc ion wi h
Li me al anodes and oxide SE is expec ed o s a om 2025 and he sul ide SE-based SSB
hen 2028.
F om an expe anking, he mos p omising concep s include P oLogium, Quan um
Scape P oLogium (NMC + Gel o Gel + Oxide elec oly e), Solid Powe , Samsung-R&D
(NMC + sulphide), and Blue Solu ions–Bollo e, Hyd o Quebec (LFP + polyme elec oly e).
The a ious company announcemen s a e summa ized in he Tables con ained in he
supplemen a y da a [135].
The analysis o companies is complica ed by he ac ha in an e o o gain a compe i-
i e ad an age in he global ma ke , many en i ies ha e elec ed o coope a ion, leading o a
me ge o companies o he c ea ion o sepa a e di isions o he esea ch and de elopmen
o solid-s a e ba e ies.
I should be also no ed ha open da a on p oduc s a e limi ed, and echnical desc ip-
ions o en lack in o ma ion, hinde ing he de elopmen o coope a ion be ween companies
and esea ch cen e s.
4. Conclusions, Rema ks and Fu u e Pe spec i es
The ansi ion o clean ene gy equi es he in oduc ion o ene gy s o age de ices
wi h excellen elec ochemical p ope ies ha espec economic, en i onmen al, and social
aspec s. Analysis o issues associa ed wi h liquid elec oly es led scien is s in he pas o
conside solid-s a e elec oly es, which made i possible o apply a me al li hium anode and
design all solid-s a e ba e ies. ASSB echnology is now a leading con ende wi h espec o
ene gy densi y and sa e y.
The pu pose o his e iew a icle was o analyze he p esence o ASSBs in he global
ma ke h ough he e olu ion o pa en s, p o o ypes and de ices p esen ed by companies,
esea ch cen e s, and uni e si ies.
Resea ch on pa en s egis e ed in he pas wo decades showed ha e e ences in hem
o ASSBs saw an exponen ial inc ease by 2021. Mos o he pa en s ela ed o solid-s a e
elec oly es, such as solid ino ganic elec oly es, whe e o emos (in e ms o he numbe o
pa en s issued las yea ) a e sul ide, ga ne and pe o ski e ypes: 196, 42, and 16 espec i ely.
The second mos popula we e solid polyme elec oly es (SPEs), wi h o e 60 pa en s,
while solid hyb id elec oly es (SHEs) appea ed in only 12 pa en s.
A lis o 93 ASSB-associa ed companies om a ound he wo ld is p o ided, based
on in o ma ion a ailable on company websi es, social media pla o ms, and in epo s
and academic publica ions. I should be no ed ha despi e he ela i ely high numbe
o manu ac u ing companies, mos o hem do no p o ide echnological in o ma ion o
pe mi e alua ion o he composi ion and e ec i eness o hei ene gy s o age de ices.
Gi en his ac , o de ailed analysis, we selec ed 35 companies ha p o ided su icien
da a on ASSB de ices in hei p oduc po olio. Acco ding o he esul s ob ained, he
USA, Japan, and China a e a he o e on o he comme cializa ion o ASSBs, and mos o
hem a ge EV applica ions wi h solid ino ganic elec oly e echnology.
Au ho Con ibu ions:
Concep ualiza ion, C.B.; me hodology, C.B. and H.F.; o mal analysis, M.V.
and A.I.; in es iga ion, C.B., N.E.K., N.J., H.F., M.V. and A.I.; da a collec ion, C.B.; w i ing—o iginal
d a p epa a ion, C.B, N.E.K., N.J. and V.P.; w i ing— e iew and edi ing, C.B., N.E.K. and V.P.;
supe ision, N.E.K. and P.S.; p ojec adminis a ion, V.P.; unding acquisi ion; All au ho s ha e ead
and ag eed o he published e sion o he manusc ip .
Ba e ies 2023,9, 157 21 o 25
Funding:
This esea ch was unded by he Technology Agency o he Czech Republic, The a P og am,
g an numbe TK03030157.
Da a A ailabili y S a emen :
The da a p esen ed in his s udy a e a ailable on eques om he
co esponding au ho .
Con lic s o In e es : The au ho s decla e no con lic o in e es .
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