Development of all-solid-state Li-ion batteries: From key technical areas to commercial use

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. 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