CN111416115A - Positive electrode for solid secondary battery, method for producing same, positive electrode assembly, and solid secondary battery - Google Patents
Positive electrode for solid secondary battery, method for producing same, positive electrode assembly, and solid secondary battery Download PDFInfo
- Publication number
- CN111416115A CN111416115A CN202010017090.0A CN202010017090A CN111416115A CN 111416115 A CN111416115 A CN 111416115A CN 202010017090 A CN202010017090 A CN 202010017090A CN 111416115 A CN111416115 A CN 111416115A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- solid electrolyte
- active material
- cathode
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007787 solid Substances 0.000 title abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 132
- 239000002245 particle Substances 0.000 claims abstract description 107
- 239000006182 cathode active material Substances 0.000 claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 claims description 86
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 150000001768 cations Chemical class 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 14
- 239000002203 sulfidic glass Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021131 SiyP3−yO12 Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910010252 TiO3 Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910008550 Li2O—Al2O3—SiO2—P2O5—TiO2—GeO2 Inorganic materials 0.000 claims description 2
- 229910009294 Li2S-B2S3 Inorganic materials 0.000 claims description 2
- 229910009305 Li2S-P2S5-Li2O-LiI Inorganic materials 0.000 claims description 2
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 claims description 2
- 229910009324 Li2S-SiS2-Li3PO4 Inorganic materials 0.000 claims description 2
- 229910009320 Li2S-SiS2-LiBr Inorganic materials 0.000 claims description 2
- 229910009316 Li2S-SiS2-LiCl Inorganic materials 0.000 claims description 2
- 229910009318 Li2S-SiS2-LiI Inorganic materials 0.000 claims description 2
- 229910009328 Li2S-SiS2—Li3PO4 Inorganic materials 0.000 claims description 2
- 229910009346 Li2S—B2S3 Inorganic materials 0.000 claims description 2
- 229910009222 Li2S—P2S5—Li2O—LiI Inorganic materials 0.000 claims description 2
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 claims description 2
- 229910007281 Li2S—SiS2—B2S3LiI Inorganic materials 0.000 claims description 2
- 229910007295 Li2S—SiS2—Li3PO4 Inorganic materials 0.000 claims description 2
- 229910007291 Li2S—SiS2—LiBr Inorganic materials 0.000 claims description 2
- 229910007288 Li2S—SiS2—LiCl Inorganic materials 0.000 claims description 2
- 229910007289 Li2S—SiS2—LiI Inorganic materials 0.000 claims description 2
- 229910007306 Li2S—SiS2—P2S5LiI Inorganic materials 0.000 claims description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 2
- 229910009709 Lia(Ni1-x-y-zCoxMnyMz)O2 Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910020215 Pb(Mg1/3Nb2/3)O3PbTiO3 Inorganic materials 0.000 claims description 2
- 229910020343 SiS2 Inorganic materials 0.000 claims description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 230000002902 bimodal effect Effects 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910018308 LaxZr1−yTiyO3 Inorganic materials 0.000 claims 1
- 229910009292 Li2S-GeS2 Inorganic materials 0.000 claims 1
- 229910009298 Li2S-P2S5-Li2O Inorganic materials 0.000 claims 1
- 229910009351 Li2S—GeS2 Inorganic materials 0.000 claims 1
- 229910009219 Li2S—P2S5—Li2O Inorganic materials 0.000 claims 1
- 239000002223 garnet Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 33
- 229910052744 lithium Inorganic materials 0.000 description 27
- 238000011068 loading method Methods 0.000 description 25
- 239000006183 anode active material Substances 0.000 description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 22
- 239000011572 manganese Substances 0.000 description 15
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000010409 thin film Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910003481 amorphous carbon Inorganic materials 0.000 description 7
- -1 transition metal sulfide Chemical class 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 229910000733 Li alloy Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000001989 lithium alloy Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000003273 ketjen black Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910000846 In alloy Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910009176 Li2S—P2 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000927 Ge alloy Inorganic materials 0.000 description 1
- 229910005842 GeS2 Inorganic materials 0.000 description 1
- 229910010854 Li6PS5Br Inorganic materials 0.000 description 1
- 229910015102 LiMnxO2x Inorganic materials 0.000 description 1
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910013124 LiNiVO4 Inorganic materials 0.000 description 1
- 229910013410 LiNixCoyAlzO2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910021466 LiQS2 Inorganic materials 0.000 description 1
- 229910012946 LiV2O5 Inorganic materials 0.000 description 1
- 229910018413 LixAlyTiz(PO4)3 Inorganic materials 0.000 description 1
- 229910016838 LixGeyPzSw Inorganic materials 0.000 description 1
- 229910014174 LixNiy Inorganic materials 0.000 description 1
- 229910014694 LixTiy(PO4)3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910020351 Pb1-xLaxZr1-yTiyO3 Inorganic materials 0.000 description 1
- 229910020345 Pb1−xLaxZr1−yTiyO3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 229910010322 TiS3 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Provided are a cathode for a solid secondary battery, a method of manufacturing the same, a cathode assembly, and a solid secondary battery, wherein the cathode includes a cathode active material and a first solid electrolyte, wherein a ratio lambda of an average particle diameter of the cathode active material to an average particle diameter of the first solid electrolyte satisfies equation 1, wherein the average particle diameter of the cathode active material is in a range of about 1 μm to about 30 μm, and the average particle diameter of the first solid electrolyte is in a range of about 0.1 μm to about 4 μm: and the equation 13 is more than or equal to lambda is less than or equal to 40.
Description
Cross reference to related applications
The present application claims the benefit of U.S. provisional patent application No.62/789,812 filed on day 8/1/2019 at the U.S. patent and trademark office, U.S. provisional patent application No.62/823,509 filed on day 25/3/2019, U.S. patent application No.16/459,896 filed on day 2/7/2019, and korean patent application No. 10-2019-.
Technical Field
The present disclosure relates to a positive electrode for a solid-state secondary battery, a method of preparing the positive electrode, a positive electrode assembly for a solid-state secondary battery including the positive electrode, and a solid-state secondary battery including the positive electrode.
Background
Solid state secondary batteries are of interest because they provide improved power density as well as improved energy density and safety.
However, there is a performance gap between currently available solid-state secondary batteries and lithium ion batteries using combustible liquid electrolytes. The safety and performance of the positive electrode in the solid-state secondary batteries developed so far have not reached a desired level, and thus there is a need for an improved solid-state lithium ion positive electrode material and a solid-state secondary battery including the same.
Disclosure of Invention
Provided is a novel positive electrode for a solid-state secondary battery.
A positive electrode assembly for a solid-state secondary battery including the positive electrode for a solid-state secondary battery is provided.
A solid-state secondary battery including the positive electrode is provided.
A method of preparing the positive electrode is provided.
Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to an aspect of an embodiment, a positive electrode for a solid-state secondary battery includes: a positive electrode active material; and a first solid electrolyte, wherein a ratio λ of an average particle diameter of the cathode active material to an average particle diameter of the first solid electrolyte satisfies equation 1, wherein the cathode active material has an average particle diameter in a range of about 1 μm to about 30 μm, and the first solid electrolyte has an average particle diameter in a range of about 0.1 μm to about 4 μm.
3≤λ≤40
According to an aspect of another embodiment, a positive electrode assembly for a solid-state secondary battery includes: the positive electrode; and a second solid electrolyte disposed on the positive electrode,
wherein the first solid electrolyte and the second solid electrolyte may be the same as or different from each other.
According to an aspect of another embodiment, a solid-state secondary battery includes: the positive electrode; a negative electrode; and a second solid electrolyte disposed between the positive electrode and the negative electrode,
wherein the first solid electrolyte and the second solid electrolyte may be the same as or different from each other. Also, the first solid electrolyte and the second solid electrolyte may be sulfide solid electrolytes, oxide solid electrolytes, or a combination thereof.
According to an aspect of another embodiment, a method of preparing a positive electrode for a solid-state secondary battery includes: providing a positive electrode active material;
providing a first solid electrolyte; and
contacting the positive electrode active material and the first solid electrolyte at a pressure in a range of about 50 megapascals (MPa) to about 600MPa to provide a positive electrode.
Drawings
The above and other aspects, features and advantages of some embodiments of the present disclosure will become more apparent from the following description considered in conjunction with the accompanying drawings, in which:
fig. 1 is a schematic diagram of a battery according to an embodiment;
fig. 2 is a graph of the ratio of positive electrode loading (weight percent, wt%) to positive electrode active material particle size (particle size) to first solid electrolyte particle size, λ, illustrating the positive electrode utilization (percent%) as a function of positive electrode loading and λ when the particle size of the positive electrode active material is in the range of about 5 μm to about 12 μm;
FIG. 3 is a graph of the ratio λ of the positive electrode loading (% by weight) to the positive electrode active material particle size to the first solid electrolyte particle size, illustrating when using 5 μm NCM and L i having a size of 1.5 μm, 3 μm, 5 μm, or 8 μm as the first solid electrolyte2P-P2S5(L PS) positive electrode utilization (%) as a function of positive electrode loading and λ;
FIG. 4 is a graph of voltage (volts, V, vs. L i-In alloy) versus capacity (mAh/g) illustrating when the cell is operated at 0.05 milliamps/square centimeter (mA/cm)2) Charge-discharge curve of battery at down-discharge, wherein the battery uses 5 μm lithium nickel cobalt manganese oxide NCM523 and 1.5 μm, 3 μmA first solid electrolyte size of m, 5 μ ι η, or 8 μ ι η, the NCM having a positive electrode loading of 60 wt% based on the total weight of the positive electrode;
fig. 5 is a graph of the ratio λ of positive electrode loading (% by weight) to positive electrode active material particle size to first solid electrolyte particle size, illustrating the positive electrode utilization (%) as a function of positive electrode loading and λ when 5 μm NCM and L PS having a 1.5 μm size as the first solid electrolyte are used;
FIG. 6 is a graph of voltage (V, versus L i-In alloy) versus capacity (mAh/g) illustrating the positive electrode loading at 0.05mA/cm for a cell using 5 μm lithium nickel cobalt manganese oxide NCM523 with the NCM having 60, 70, or 80 weight percent positive electrode loading based on the total weight of the positive electrode2A discharge voltage at the time of lower discharge, in which the first solid electrolyte has a size of 1.5 μm and the ratio λ is 3.3;
fig. 7 is a graph of positive electrode loading (% by weight) versus the ratio of positive electrode active material particle size to first solid electrolyte particle size, λ, illustrating positive electrode utilization (%), as a function of positive electrode loading and λ; and
fig. 8 is a graph of positive active material loading (% by volume, vol%) versus positive loading (% by weight) and the amount of the first solid electrolyte (% by weight) when the porosity is 0%, 10%, and 20%.
The above described and other features are exemplified by the following figures and detailed description.
Detailed Description
Reference will now be made in detail to the embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as limited to the descriptions set forth herein. Accordingly, the embodiments are described below to illustrate aspects only by referring to the drawings. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Expressions such as "at least one (one) of … … modify the entire list of elements when preceding or succeeding the list of elements rather than modifying individual elements of the list.
Hereinafter, a solid-state positive electrode, a method of preparing the positive electrode, and a battery including the positive electrode according to embodiments will be described in detail.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the inventive concept. The use of the singular forms "a", "an" and "the" encompass plural referents unless the context clearly dictates otherwise.
As used herein, it will be understood that terms such as "comprising," "having," and "including" are intended to mean that there are features, numbers, steps, actions, components, elements, components, regions, materials, or combinations thereof disclosed in the specification, and are not intended to preclude the possibility that one or more other features, numbers, steps, actions, components, elements, components, regions, materials, or combinations thereof may be present or may be added. As used herein, the term "or" may be interpreted as "and" or "depending on the context.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the drawings, the thickness of layers and regions are exaggerated for clarity. Like reference symbols in the various drawings indicate like elements. It will be understood that when an element such as a layer, film, region, or panel is referred to as being "on" another element, it can be directly on the other element or intervening elements may be present. It will be understood that, although terms such as "first," "second," etc. may be used to describe various components, such components are not necessarily limited to the above terms. The above terms are only used to distinguish one component from another component.
Solid-state secondary batteries are of interest because they do not have the safety issues associated with liquid electrolytes and provide higher energy densities than liquid electrolytes. However, effects not present in lithium secondary batteries using liquid electrolytes, such as degradation of solid electrolytes caused by reaction of solid electrolytes with conductive diluents used in positive electrodes developed for liquid electrolytes, highlight use in solid lithium or lithium ion batteriesThus, materials developed for lithium or lithium ion batteries using liquid electrolytes, particularly those using lithium nickel oxide positive electrode active materials, such as those of formula L i1+x(Ni1-x-y- zCoyMnz)1-zO2Has been shown to be unsuitable for use in solid state lithium or lithium ion batteries.
Recently, publications have taught the use of small particle size NCM positive electrode active materials, such as D50 particle size of less than 4 μm, to overcome charge transport limitations. While not wishing to be bound by theory, it is understood that charge transport limitations in positive electrode active materials, such as NCM, encourage the use of small particle sizes, such as 4 μm or less, when considered alone. It has been found that the interaction between the positive electrode active material and the solid electrolyte is often more important than the charge transport limitation in the positive electrode active material. In detail, it has been found that ion transport limitation at the particle surface and between the positive electrode active material particles and the solid electrolyte particles is so important that improved performance can be provided by using a selected combination of positive electrode active material particle size and solid electrolyte particle size, particularly when using a nickel-containing positive electrode active material such as NCM. In particular, and while not wishing to be bound by theory, this interaction indicates that the use of a positive electrode active material having a relatively large particle size in combination with a solid electrolyte may provide improved performance when a positive electrode active material, such as NCM, is used in combination with the solid electrolyte.
A positive electrode for a solid-state secondary battery is provided. The positive electrode includes a positive electrode active material and a first solid electrolyte, wherein a ratio λ of an average particle diameter of the positive electrode active material to an average particle diameter of the first solid electrolyte satisfies equation 1, wherein the average particle diameter of the positive electrode active material is in a range of about 1 μm to about 30 μm, and the average particle diameter of the first solid electrolyte is in a range of about 0.1 μm to about 4.0 μm:
3≤λ≤40。
A ratio λ of an average particle diameter of the cathode active material to an average particle diameter of the first solid electrolyte is in a range of about 3.3 to about 8, for example, about 4 to about 8.
In an embodiment, the average particle size of the positive electrode active material is in a range of about 5 μm to about 12 μm, the average particle size of the first solid electrolyte is in a range of about 1.5 μm to about 4 μm, and the amount of the positive electrode active material is in a range of about 70 weight percent (wt%) to about 85 wt%, based on the total weight of the positive electrode.
When a positive electrode active material having a large average particle diameter of about 4 μm or more is used in combination with a solid electrolyte having a relatively small particle size, the performance of the solid-state secondary battery can be improved. When the average particle diameter of the cathode active material, the average particle diameter of the first solid electrolyte, and the amount of the cathode active material are within these ranges, a cathode having a high energy density can be prepared even when a cathode active material having a large average particle diameter of about 4 μm or more is used.
The positive active material may include a lithium transition metal oxide and a transition metal sulfide. For example, the positive active material may be a lithium composite oxide including lithium and a metal selected from cobalt, manganese, and nickel. For example, the positive electrode active material may be selected from compounds represented by the following formulae:
LipM1 l-qM2 qD2(wherein p is 0.90-1.8 and q is 0-0.5); L ipEl-qM2 qO2-xDx(wherein p is 0.90. ltoreq. p.ltoreq.1.8, q is 0. ltoreq. q.ltoreq.0.5, and x is 0. ltoreq. x.ltoreq.0.05) L iE2-qM2 qO4-xDx(wherein q is 0-0.5 and x is 0-0.05); L ipNi1-q- rCoqM2 rDx(wherein p is 0.90. ltoreq. p.ltoreq.1.8, q is 0. ltoreq. q.ltoreq.0.5, r is 0. ltoreq. r.ltoreq.0.05, and 0<x≤2)；LipNi1-q-rCopM2 rO2-xXx(wherein p is 0.90. ltoreq. p.ltoreq.1.8, q is 0. ltoreq. q.ltoreq.0.5, r is 0. ltoreq. r.ltoreq.0.05, and 0<x<2)；LipNi1-q-rMnqM2 rDx(wherein p is 0.90. ltoreq. p.ltoreq.1.8, q is 0. ltoreq. q.ltoreq.0.5, r is 0. ltoreq. r.ltoreq.0.05, and 0<x≤2)；LipNi1-q-rMnqM2 rO2-xXx(wherein p is 0.90. ltoreq. p.ltoreq.1.8, q is 0. ltoreq. q.ltoreq.0.5, r is 0. ltoreq. r.ltoreq.0.05, and 0<x<2)；LipNiqErGdO2L i (wherein p is 0.90-1.8, q is 0-0.9, r is 0-0.5, and d is 0.001-0.1)pNiqCorMndGeO2(wherein p is 0.90-1.8, q is 0-0.9, r is 0-0.5, d is 0-0.5, and e is 0.001-0.1)pNiGqO2(wherein p is 0.90-1.8 and q is 0.001-0.1); L ipCoGqO2(wherein p is 0.90-1.8 and q is 0.001-0.1); L ipMnGqO2(wherein p is 0.90-1.8 and q is 0.001-0.1); L ipMn2GqO4(wherein p is more than or equal to 0.90 and less than or equal to 1.8 and q is more than or equal to 0.001 and less than or equal to 0.1); QO2；QS2；LiQS2；V2O5；LiV2O5；LiRO2；LiNiVO4；Li(3-f)J2(PO4)3(where 0. ltoreq. f. ltoreq.2); L i(3-f)Fe2(PO4)3(where 0. ltoreq. f. ltoreq.2), and L iFePO4。
In the formula, M1Is Ni, Co, or Mn; m2Is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V or rare earth elements, D is O, F, S or P, E is Co or Mn, X is F, S or P, G is Al, Cr, Mn, Fe, Mg, L a, Ce, Sr or V, Q is Ti, Mo or Mn, R is Cr, V, Fe, Sc or Y, and J is V, Cr, Mn, Co, Ni or Cu.
Examples of the positive active material may include L iCoO2、LiMnxO2x(wherein x is 1 or 2), L iNi1-xMnxO2(wherein 0)<x<1)、LiNi1-x-yCoxMnyO2(wherein x is more than or equal to 0 and less than or equal to 0.5 and y is more than or equal to 0 and less than or equal to 0.5), L iFePO4、TiS2、FeS2、TiS3、FeS3Or a combination thereof.
In an embodiment, the positive active material may include, for example, lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, or a combination thereof.
The positive electrode active material may be, for example, an NCA or NCM material represented by formula 1:
LixNiyEzGdO2
In formula 1, 0.90 ≦ x ≦ 1.8, 0 ≦ y ≦ 0.9, 0 ≦ z ≦ 0.5, 0.001 ≦ d ≦ 0.5, 0.001 ≦ y + z + d ≦ 1, E is Co, and G is Al, Cr, Mn, Fe, Mg, L a, Ce, Sr, V, or a combination thereof, e.g., y + z + d is 1.
In formula 1, y is 0.5, E is Co, G is Mn, z is 0.2, and d is 0.3, examples of the positive electrode active material may include L iNi0.5Co0.2Mn0.3O2(NCM) and L iNi0.5Co0.3Mn0.2O2。
The positive electrode active material may be, for example, a nickel-based active material represented by formula 2.
Lia(Ni1-x-y-zCoxMnyMz)O2
In formula 2, M is an element selected from the group consisting of: boron (B), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr), and aluminum (Al),
and 0.95. ltoreq. a.ltoreq.1.3, 0< x <1, 0. ltoreq. y <1, and 0. ltoreq. z < 1.
The positive active material may be, for example, a compound of formula 3, a compound of formula 4, or a combination thereof.
LiNixCoyAlzO2
In formula 3, 0< x <1, 0< y <1, 0< z <1, and x + y + z ═ 1.
LiNixCoyMnzO2
In formula 4, 0< x <1, 0< y <1, 0< z <1, and x + y + z ═ 1.
In formulas 3 and 4, x may range, for example, from about 0.7 to about 0.99, from about 0.75 to about 0.95, from about 0.8 to about 0.95, or from about 0.85 to about 0.95. In formulas 3 and 4, when x is within these ranges, the amount of nickel of the positive electrode active material may be in the range of about 70 mol% to about 99 mol%.
The positive electrode active material may be covered with a coating layer, the coating layer may be any material used as a coating layer of a solid secondary battery in the art, the coating layer may be, for example, L i2O-ZrO2。
The positive electrode may include a positive electrode active material and a first solid electrolyte. In one embodiment, the positive electrode may be composed of a positive electrode active material and a first solid electrolyte.
The positive electrode may include, for example, additives such as a conductive agent, a binder, a filler, a dispersant, an ion conductive agent, in addition to the positive electrode active material and the solid electrolyte. Examples of the conductive agent may include graphite, carbon black, acetylene black, ketjen black, carbon fiber, and metal powder. Examples of the binder may include Styrene Butadiene Rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, and polyethylene. The filler, the dispersant and the ion-conducting agent that may be added to the positive electrode may be materials commonly used in electrodes of solid secondary batteries.
The first solid electrolyte may include a sulfide solid electrolyte, and an example of the sulfide solid electrolyte may include L i2S-P2S5、Li2S-P2S5-L iX (wherein X is a halogen element), L i2S-P2S5-Li2O、Li2S-P2S5-Li2O-LiI、Li2S-SiS2、Li2S-SiS2-LiI、Li2S-SiS2-LiBr、Li2S-SiS2-LiCl、Li2S-SiS2-B2S3-LiI、Li2S-SiS2-P2S5-LiI、Li2S-B2S3、Li2S-P2S5-ZmSn(wherein m and n are positive numbers and Z is one of Ge, Zn, or Ga), L i2S-GeS2、Li2S-SiS2-Li3PO4、Li2S-SiS2-LipM1Oq(wherein p and q are positive numbers, M1P, Si, Ge, B, Al, Ga, or In), L i7-xPS6-xClx(wherein 0)<x<2)、Li7-xPS6-xBrx(wherein 0)<x<2) Or L i7-xPS6-xIx(wherein 0)<x<2)。
When L i2S-P2S5L i when used as a sulfide solid electrolyte for forming the solid electrolyte2S and P2S5May be in the range of about 50:50 to about 90:10 (L i)2S:P2S5)。
The sulfide solid electrolyte may be, for example, a digermorite-type compound including at least one selected from L i7-xPS6-xClx(where 0. ltoreq. x. ltoreq.2), L i7-xPS6-xBrx(wherein 0. ltoreq. x. ltoreq.2), and L i7-xPS6-xIx(wherein 0. ltoreq. x. ltoreq.2.) specifically, the sulfide solid electrolyte may be a thiogermorite-type compound including at least one selected from L i6PS5Cl、Li6PS5Br, and L i6PS5I。
The density of the digermorite-type solid electrolyte may range from about 1.5g/cc to about 2.0 g/cc. When the digermite-type solid electrolyte has a density of at least 1.5g/cc, the internal resistance of the solid-state secondary battery can be reduced, and the penetration of lithium into the solid electrolyte layer can be effectively suppressed.
In further embodiments, the sulfide solid electrolyte may be a compound represented by formula 5.
(Li1-xM1x)7-yPS6-yM2y
In formula 5, x and y can be 0< x.ltoreq.0.07 and 0. ltoreq.y.ltoreq.2.
In formula 5, for example, M1 can be Na, K, or a combination thereof; and M2 can be F, Cl, Br, I, or a combination thereof.
The compound of formula 5 may have 1x10-5S/cm or higher, e.g. 1X10-41x10 of S/cm or higher-3S/cm or higher, or 1x10-3An ion conductivity of S/cm to 20S/cm. The sulfide solid electrolyte has both stability to metallic lithium and high ion conductivity.
Examples of the compound of formula 5 may include (L i)5.6925Na0.0575)PS4.75Cl1.25、(Li5.445Na0.055)PS4.5Cl1.5、(Li5.148Na0.052)PS4.2Cl1.8And (L i)5.8905Na0.0595)PS4.95Cl1.05。
The first solid electrolyte may be an oxide solid electrolyte.
The first solid electrolyte may be, for example, L i1+x+yAlxTi2-xSiyP3-yO12(wherein 0)<x<2 and 0. ltoreq. y<3)、BaTiO3、Pb(Zr(1-x)Tix)O3(wherein x is more than or equal to 0 and less than or equal to 1) and Pb1-xLaxZr1-yTiyO3(wherein 0. ltoreq. x<1 and 0. ltoreq. y<1)、Pb(Mg1/ 3Nb2/3)O3-PbTiO3、HfO2、SrTiO3、SnO2、CeO2、Na2O、MgO、NiO、CaO、BaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2、SiO2、SiC、Li3PO4、LixTiy(PO4)3(wherein 0)<x<2 and 0<y<3)、LixAlyTiz(PO4)3(wherein 0)<x<2，0<y<1, and 0<z<3)、Li1+x+y(Al(1-m)Gam)x(Ti(1-n)Gen)2-xSiyP3-yO12(wherein x is 0. ltoreq. x.ltoreq.1, y is 0. ltoreq. y.ltoreq.1, m is 0. ltoreq. m.ltoreq.1, and n is 0. ltoreq. n.ltoreq.1), L ixLayTiO3(wherein 0)<x<2 and 0<y<3)、LixGeyPzSw(wherein 0)<x<4，0<y<1，0<z<1, and 0<w<5)、LixNy(wherein 0)<x<4 and 0<y<2)、SiS2、LixSiySz(wherein 0)<x<3，0<y<2, and 0<z<4)、LixPySz(wherein 0)<x<3，0<y<3, and 0<z<7)、Li2O、LiF、LiOH、Li2CO3、LiAlO2、Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2Ceramic, formula L i3+xLa3M1 2O12(wherein M is1Te, Nb, or Zr, and x is an integer of 1 to 10), a compound of formula 5, or a combination thereof.
(Li1-xM1x)7-yPS6-yM2y
In formula 5, 0< x ≦ 0.07, 0 ≦ y ≦ 2, M1 is Na, K, or a combination thereof, and
m2 is F, Cl, Br, I, or a combination thereof.
The oxide solid electrolyte may be, for example, (L a)1-xLix)TiO3(LL TO) (where 0<x<1)。
The oxide solid electrolyte may be, for example, a compound represented by formula 6.
Li5+xE3(Me1 zMe2 (2-z))Od
In formula 6, E is a trivalent cation, Me1And Me2Each independently is one of: trivalent cation, tetravalent cation, pentavalent cation, and hexavalent cation, wherein 0<x is less than or equal to 3 and z is less than or equal to 0<2, and 0<d is less than or equal to 12; o may optionally be pentavalentThe anion, hexavalent anion, heptavalent anion, or combinations thereof are partially or fully replaced.
For example, E may be partially replaced by a monovalent or divalent cation.
In another embodiment, for example, in formula 6, when 0<When x is less than or equal to 2.5, E can be L a, and Me2May be Zr.
In one embodiment, the oxide may be a compound represented by formula 7.
Formula 7
Li5+x+2y(DyE3-y)(Me1 zMe2 2-z)Od
In formula 7, D is a monovalent or divalent cation; e is a trivalent cation; me1And Me2Each independently is a trivalent, tetravalent, pentavalent, or hexavalent cation; 0<x+2y≤3，0≤y≤0.5，0≤z<2, and 0<d is less than or equal to 12; and O may optionally be partially or fully replaced by a pentavalent anion.
The molar number of lithium in the above formula is 6< (5+ x +2y) <7.2, 6.2< (5+ x +2y) <7, or 6.4< (5+ x +2y) < 6.8.
In formulas 6 and 7, the anion has a valence of-1, -2, or-3.
In the garnet-type oxide of the above formula, D may be potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), barium (Ba), or strontium (Sr). In one embodiment, D may be calcium (Ca), barium (Ba), or strontium (Sr).
In the above formula, Me1And Me2May be a metal. For example, Me1And Me2L i can be provided for tantalum (Ta), niobium (Nb), yttrium (Y), scandium (Sc), tungsten (W), molybdenum (Mo), antimony (Sb), bismuth (Bi), hafnium (Hf), vanadium (V), germanium (Ge), silicon (Si), aluminum (Al), gallium (Ga), titanium (Ti), cobalt (Co), indium (In), zinc (Zn), or chromium (Cr)6.5La3Zr1.5Ta0.5O12。
Improved performance of the solid state secondary battery may be provided when the ratio of the average particle size of the cathode active material to the average particle size of the first solid electrolyte is 3 ≦ λ ≦ 40, wherein the cathode active material has an average particle size in a range of about 1 μm to about 30 μm, or, for example, about 5 μm to about 20 μm, and wherein the first solid electrolyte has an average particle size in a range of about 0.1 μm to about 4 μm. As described above, contrary to the prior teachings, the use of a relatively large positive electrode active material particle size in combination with a relatively small particle size solid electrolyte may provide improved performance.
The average particle size of the positive electrode active material may be in a range of about 1 μm to about 30 μm, about 2 μm to about 25 μm, about 4 μm to about 20 μm, about 5 μm to about 20 μm, about 6 μm to about 18 μm, about 8 μm to about 16 μm, or about 10 μm to about 14 μm. The first solid electrolyte may have an average particle size in a range from about 0.1 μm to about 4 μm, from about 0.1 μm to about 3.8 μm, from about 0.2 μm to about 3.6 μm, from about 0.3 μm to about 3.4 μm, from about 0.4 μm to about 3.2 μm, or from about 0.5 μm to about 3 μm. When the positive electrode active material and the first solid electrolyte have sizes within these ranges, improved performance of the solid-state secondary battery may be provided.
As used herein, the term "average particle size", "average particle size" or "D50 particle size" refers to a particle size corresponding to 50% of the particles in a distribution curve in which the particles accumulate in order of particle size from the smallest to the largest particles, and the total number of accumulated particles is 100%. For example, the average particle size can be measured by methods known to those skilled in the art. For example, the average particle size can be determined by, for example, dynamic light scattering using a commercially available particle size analyzer, or can be measured using a Transmission Electron Microscope (TEM) or a Scanning Electron Microscope (SEM). When the average particle size is measured using TEM or SEM, the value obtained from the average longest particle can be used as the average particle size. Herein, the average longest particle may refer to, for example, the particle having the longest length of the longitudinal axis.
In one embodiment, the particle size distribution of the combination of the positive electrode active material and the first solid electrolyte is a bimodal distribution. The particle distribution of the positive electrode active material and the first solid electrolyte may have, for example, a trimodal or multimodal distribution. The particle size and particle size distribution may be provided by ball milling, jet milling, grinding, sieving, or combinations thereof.
In an embodiment, the amount of the cathode active material in the cathode, for example, the loading of the cathode active material in the cathode, may be in a range of about 60 wt% to about 95 wt%, about 60 wt% to about 90 wt%, about 65 wt% to about 88 wt%, about 70 wt% to about 85 wt%, or about 80 wt% to about 85 wt%, based on the total weight of the cathode. In one embodiment, the amount of the cathode active material in the cathode, for example, the loading of the cathode active material in the cathode, may be in a range of about 60 wt% to about 75 wt%, or about 60 wt% to about 70 wt%, based on the total weight of the cathode. While not wishing to be bound by theory, it is understood that the use of a combination of the positive electrode active material and the particle size of the first solid electrolyte allows for the amount of the positive electrode active material used in the positive electrode.
In an embodiment, the porosity of the positive electrode active material may be less than 25% or, for example, in a range of about 0.01% to about 25%, about 0.1% to about 20%, about 0.5% to about 15%, or about 1% to about 10%, based on the total volume of the positive electrode. While not wishing to be bound by theory, it is understood that the use of a combination of the positive electrode active material and the particle size of the first solid electrolyte allows the porosity to be used and may provide improved performance such as specific capacity, energy density, or power density. When the combination of the particle sizes of the positive electrode active material and the first solid electrolyte is used, the bulk density may be improved, and thus the specific energy and energy density may be improved.
The porosity of the cathode active material may be measured by mercury intrusion method, such as analysis of TEM, SEM, or cross-sectional analysis of particles using Focused Ion Beam (FIB).
Also, the amount of the positive electrode active material may range from about 30 vol% to about 80 vol%, or, for example, from about 35 vol% to about 75 vol%, or from about 40 vol% to about 70 vol%, based on the total volume of the positive electrode.
Also, in the cathode, the amount of the first solid electrolyte may be in a range of about 10 wt% to about 40 wt%, or, for example, about 15 wt% to about 35 wt%, or about 20 wt% to about 25 wt%, based on the total weight of the cathode. When the amount of the first solid electrolyte is within these ranges, a larger amount of the positive electrode active material may be used, and thus the specific capacity and energy density may be increased.
The utilization rate of the positive electrode according to the embodiment may be about 80% or more, or, for example, about 82% or more, or in the range of about 82% to about 99% or, for example, about 82% to about 95%. The definition of the utilization of the positive electrode is the same as generally known in the art. The utilization rate of the positive electrode indicates a ratio that contributes to capacity in the entire positive electrode, or may refer to, for example, a percentage of the amount of the positive electrode active material with respect to the total amount of the positive electrode. Herein, the term "amount" may mean weight.
Alternatively, the utilization of the positive electrode can be defined by the following equation 2.
Positive electrode utilization ratio (%) { (actual capacity of positive electrode/theoretical capacity of positive electrode active material) } X100
In the positive electrode for a solid secondary battery, the positive electrode active material may be a transition metal oxide including nickel, cobalt, and manganese, and when the positive electrode is at a temperature of 25 ℃ and 0.05mA/cm2The capacity of the positive electrode active material may be in a range of about 110mAh/g to about 220mAh/g or, for example, about 110mAh/g to about 150mAh/g when discharged at a current density of (a).
The positive electrode may further include at least one selected from the group consisting of a conductive agent and a binder. Examples of the conductive agent may include:
graphite, carbon black, acetylene black, ketjen black, Carbon Nanotubes (CNTs), carbon fibers, metallic materials such as Ni, or combinations thereof.
Examples of the binder may include Styrene Butadiene Rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or a combination thereof.
The positive electrode may further include additives such as a filler, a coating agent (a covering agent), a dispersant, and an ion conductive agent, in addition to the positive electrode active material, the solid electrolyte, the binder, and the conductive agent.
The filler, the coating agent (covering agent), the dispersant, and the ion conductive agent that may be added to the positive electrode may be materials commonly used in an electrode of a solid secondary battery.
The improved electrode may provide improved performance of the solid state secondary battery.
In one embodiment, the positive electrode may have an improved specific energy.
According to another embodiment, the positive active material is a transition metal oxide comprising nickel and cobalt. The positive active material provides a capacity in a range of about 110mAh/g to about 175mAh/g, or, for example, about 120mAh/g to about 165mAh/g, or about 130mAh/g to about 155mAh/g, when a unit cell including the positive electrode is discharged at a C/20 rate at 25 ℃, based on the total weight of the positive active material.
In some embodiments, a unit cell including the positive electrode may be charged at 25 ℃ at a rate of C/20 to L i/L i+4.2 volts (V) and then discharged at 25 ℃ at a C/20 rate to L i/L i+To measure capacity.
Also, there is provided a positive electrode assembly for a solid secondary battery, the assembly including: the positive electrode; and a second solid electrolyte on the positive electrode, wherein the first solid electrolyte and the second solid electrolyte are the same as or different from each other.
For example, the second solid electrolyte is a sulfide solid electrolyte, an oxide solid electrolyte, or a combination thereof.
In one embodiment, the first solid electrolyte and the second solid electrolyte are the same solid electrolyte. In some embodiments, the first solid electrolyte and the second solid electrolyte are different electrolytes.
In some embodiments, the first solid electrolyte may be L i2S-P2S5And is andthe second solid electrolyte may be a garnet-type material, such as L i7La3Zr2O12。
Also, a solid-state secondary battery is provided. As shown in fig. 1, the solid-state secondary battery 200 includes a cathode 210, an anode 240, and a second solid electrolyte 220 between the cathode 210 and the anode 240, wherein the first solid electrolyte and the second solid electrolyte are the same as or different from each other. For example, a separator 230 may be optionally included in the solid secondary battery 200. The solid secondary battery 200 includes a case 250 and a top cap 260.
The negative electrode may include a negative active material.
Examples of the negative active material may include lithium metal, lithium alloy, and any material that can reversibly absorb and desorb lithium or intercalate and deintercalate lithium. Examples of the negative active material may include lithium metal, lithium alloy, or lithium compounds such as lithium titanium oxide, and carbonaceous negative active materials.
The negative active material may be disposed on a current collector, such as a copper current collector.
The carbonaceous anode active material is specifically amorphous carbon. Examples of the amorphous carbon may include Carbon Black (CB), Acetylene Black (AB), Furnace Black (FB), Ketjen Black (KB), or graphene, but the embodiment is not limited thereto, and any amorphous carbon available in the art may be used. The amorphous carbon refers to carbon having no crystallinity or very low crystallinity, and is different from crystalline carbon or graphite-based carbon.
In some embodiments, the negative active material may be any metal or semi-metal active material in the art that forms an alloy or compound with lithium. For example, the anode active material may include at least one selected from the group consisting of: gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn).
The negative electrode may include a negative active material layer.
The anode active material layer may include one type of anode active material or a plurality of different types of anode active materials.
For example, the anode active material layer may include amorphous carbon alone or a mixture including amorphous carbon and at least one selected from the group consisting of: gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn). The mixing ratio of the mixture of amorphous carbon and gold in the mixture may be a weight ratio in the range of about 10:1 to about 1:2, about 5:1 to about 1:1, or about 4:1 to about 2: 1.
When the mixture is used as an anode active material, the cycle characteristics of the solid-state secondary battery can be further improved.
For example, the anode active material layer may include a binder. Examples of the binder may include styrene-butadiene rubber (SBR), Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene, vinylidene fluoride/hexafluoropropylene copolymer, polyacrylonitrile, polymethylmethacrylate, but the embodiment is not limited thereto, and any binder available in the art may be used.
The negative active material layer is disposed on a current collector, such as a copper current collector.
For example, the solid secondary battery may further include a thin film on the negative electrode current collector, the thin film including an element that can form an alloy with lithium. The film is disposed between the negative electrode current collector and the negative electrode active material layer. For example, the thin film may include an element that can form an alloy with lithium. Examples of the element that can form an alloy with lithium may include gold, silver, zinc, tin, indium, silicon, aluminum, and bismuth. The thin film is formed of one of these metals, or may be formed of an alloy of different metals. For example, when the thin film is disposed on the anode current collector, the shape of a precipitate (not shown) of the anode active material layer precipitated between the thin film and the anode active material layer is further flattened, and the cycle characteristics of the solid-state secondary battery can be further improved.
The thickness of the thin film may range from about 1nm to about 800nm, or for example from about 50nm to about 600nm, or from about 100nm to about 500 nm. When the thickness of the thin film is within these ranges, the amount of lithium precipitation in the anode may increase as the thin film intercalates lithium, which may result in an increase in the energy density of the solid state secondary battery, and thus the cycle characteristics of the solid state secondary battery may be improved. The thin film may be disposed on the anode current collector by using, for example, vacuum vapor deposition, sputtering, or plating, but the embodiment is not limited thereto.
The solid-state secondary battery according to the embodiment may further include, for example, a second anode active material layer disposed between the anode current collector and the second solid electrolyte by charging. In some embodiments, the solid-state secondary battery may further include, for example, a second negative electrode active material layer disposed between the negative electrode current collector and the first negative electrode active material layer by charging. In some embodiments, the solid-state secondary battery may further include, for example, a second anode active material layer disposed between the solid electrolyte layer and the first anode active material layer by charging.
Accordingly, since the second negative electrode active material layer is a metal layer including lithium, the second negative electrode active material layer serves as, for example, a lithium reservoir, examples of the lithium alloy may include L i-Al alloy, L i-Sn alloy, L i-In alloy, L i-Ag alloy, L i-Au alloy, L i-Zn alloy, L i-Ge alloy, and L i-Si alloy, but embodiments are not limited thereto, and any lithium alloy available In the art may be used.
For example, the second anode active material layer may be disposed between the anode current collector and the first anode active material layer before the solid-state secondary battery is assembled, or may be deposited between the anode current collector and the first anode active material layer by charging after the solid-state secondary battery is assembled.
When the second anode active material layer is disposed between the anode current collector and the first anode active material layer before the solid-state secondary battery is assembled, the second anode active material layer is a metal layer including lithium, and thus the second anode active material layer may serve as a lithium reservoir. The cycle characteristics of the solid-state secondary battery including the second anode active material layer may be further improved. A lithium foil may be disposed between the negative electrode current collector and the first negative electrode active material layer before the solid-state secondary battery is assembled.
When the second anode active material layer is provided by charging after the solid-state secondary battery is assembled, the solid-state secondary battery does not include the second anode active material layer at the time of assembling the solid-state secondary battery, and thus the energy density of the solid-state secondary battery increases.
In some embodiments, the negative electrode may be a lithium-free region that does not include lithium metal or a lithium alloy in an initial state of the battery or after discharging the battery.
According to another embodiment, a method of preparing the positive electrode is provided.
The method comprises the following steps: providing a positive electrode active material; providing a first solid electrolyte; and
contacting the positive electrode active material and the first solid electrolyte at a pressure in a range of about 50MPa to about 600MPa to provide the positive electrode. The contacting of the positive electrode active material and the first solid electrolyte may be provided by using, for example, a press or a hammer mill.
When the positive electrode active material and the first solid electrolyte are brought into contact under a pressure in the range of about 50MPa to about 600MPa, the positive electrode can be prepared in a desired shape when the pressure is in this range.
The positive electrode active material and the first solid electrolyte may be brought into contact with each other by using a mechanical milling method.
Providing the positive electrode may include, for example, adding a binder to a mixture of the positive electrode active material and the first solid electrolyte. A conductive agent may be added to the mixture.
In one embodiment, the solid-state secondary battery may be provided by: further comprising disposing a second solid electrolyte layer between the positive electrode and the negative electrode. A separator may be prepared between the positive electrode and the negative electrode. For example, the separator may be a microporous material optionally including a second solid electrolyte.
One or more embodiments will now be described in more detail with reference to the following examples. However, these examples are not intended to limit the scope of the one or more implementations.
Examples
Example 1: particle size ratio
The particle size ratio was evaluated by using the positive electrode active material L iNi having a particle size of 5 μm0.5Co0.2Mn0.3O2(NCM523) or a positive electrode active material NCM523 having a particle size of 12 μm and L i as a first solid electrolyte having a particle size in the range of about 1.25 μm to about 8 μm2S-P2S5(L PS, where L i2S and P2S5At a molar ratio of 7:3) to determine the positive electrode utilization. The ratio λ of the particle size of the positive electrode active material to the particle size of the first solid electrolyte is in the range of about 0.625 to about 8.
The positive utilization is defined the same as in equation 2.
Positive electrode utilization ratio (%) { (actual capacity of positive electrode/theoretical capacity of positive electrode active material) } X100
Fig. 2 is a graph of the positive electrode loading (weight percent, wt% of positive electrode active material based on the total weight of the positive electrode) versus the ratio of the positive electrode active material particle size to the first solid electrolyte particle size, λ. In fig. 2, the positive electrode utilization is in the range of about 1 to about 0.1. As shown in fig. 2, the positive electrode utilization rate is related to the ratio λ. When λ is less than 1, it is difficult to achieve a positive electrode utilization ratio of more than 50%. When λ is 3 or greater, using a positive electrode load of 70 wt% or less provides a positive electrode utilization of 82% or greater.
Example 2: effect of first solid electrolyte particle size
Using NCM523 having a particle size of 5 μm, confirmation was madeFIG. 3 is a graph of cathode loading using L PS first solid electrolyte having a particle size in the range of about 1.25 μm to about 8 μm (% by weight of cathode active material based on the total weight of the cathode) versus the ratio of cathode active material particle size to first solid electrolyte particle size λ FIG. 3 provides a cathode utilization of about 82% or greater at a cathode loading of 60% by weight, as shown in FIG. 3, FIG. 4 shows 0.05mA/cm for a cathode using L PS having a particle size of 1.5 μm, 3 μm, 5 μm, or 8 μm and 5 μm NCM532 having a particle size of 5 μm2The discharge curve shown in fig. 4 corresponds to the point indicated in fig. 3 at a positive electrode load of 60 wt% and at 8 μm, 5 μm, 3 μm, or 1.5 μm the discharge curve shown in fig. 4 is obtained by applying a battery including lithium metal as a negative electrode and L PS as a solid electrolyte.
Example 3: positive loading effect
The ratio λ was further evaluated using NCM 532L PS with a particle size of 5 μm and L PS with a particle size of 1.5 μm as the first solid electrolyte with various positive electrode loadings the ratio λ was 3.3 as shown in fig. 5, when the ratio λ was 3.3, up to 70 wt% of the positive electrode loading was used and the utilization rate was about 82% or more, the NCM523 with a particle size of 5 μm and L i with a particle size of 1.5 μm as the first solid electrolyte were used at various NCM523 loadings of 60%, 70% and 80%7P3S11The discharge curve of the battery of (a) is shown in fig. 6. As shown in fig. 6, at 70 wt% NCM523 and λ 3.3, the capacity was about 150mAh/g or higher. Using 0.05mA/cm at 25 DEG C2The discharge curve shown in fig. 6 was obtained by applying a battery including lithium metal as the negative electrode and L PS as the solid electrolyte.
Example 4: first solid electrolyte content and porosity
The effect of the ratio λ is shown in fig. 7, which illustrates the positive electrode utilization when using various combinations of NCM532 and L PS particle sizes, and the ratio is in the range of about 1 to about 8, as shown in fig. 7, the utilization is 80% or higher when the positive electrode loading is 80% by weight, e.g., 50% by volume, here, the ratio λ is 4, as shown in fig. 8, when using the combination of the positive electrode active material and the first solid electrolyte particle size, the amount of the positive electrode active material increases, and the amount of the solid electrolyte decreases, and thus the positive electrode active material loading increases, which improves the effect at low porosity, e.g., 20%, 10%, or 0% porosity, "0.12" in fig. 8 shows a porosity of 12%, and "0.1" shows a porosity of 10%, in fig. 8, the sum of the solid electrolyte content and the positive electrode loading is 95%, and the remaining 5% is the content of CNF (carbon nanofiber).
As described above, according to one or more embodiments, a positive electrode for a solid-state secondary battery and a solid-state secondary battery including the same having improved properties such as energy density may be prepared by using a positive electrode active material having a large particle size and a solid electrolyte having a small particle size in combination.
Various embodiments are shown in the drawings.
It is to be understood that the embodiments described herein are to be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects in various embodiments should typically be considered as available for other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope defined by the following claims.
Claims (21)
1. A positive electrode for a solid-state secondary battery, the positive electrode comprising:
a positive electrode active material; and
a first solid electrolyte, which is a solid electrolyte,
wherein a ratio λ of an average particle diameter of the positive electrode active material to an average particle diameter of the first solid electrolyte satisfies equation 1,
wherein the average particle diameter of the positive electrode active material is in a range of 1 μm to 30 μm, and the average particle diameter of the first solid electrolyte is in a range of 0.1 μm to 4 μm:
equation 1
3≤λ≤40。
2. The cathode of claim 1, wherein the amount of the cathode active material ranges from 60 weight percent (wt%) to 90 wt%, based on the total weight of the cathode.
3. The cathode of claim 2, wherein the porosity of the cathode is 25% or less based on the total volume of the cathode.
4. The cathode of claim 3, wherein the amount of the cathode active material is in a range of 30 volume percent (vol%) to 80 vol%, based on the total weight of the cathode.
5. The cathode of claim 3, wherein the amount of the first solid electrolyte ranges from 10 wt% to 40 wt% based on the total weight of the cathode.
6. The cathode of claim 3, wherein the particle size distribution of the cathode active material and the first solid electrolyte has a bimodal distribution.
7. The cathode of claim 1, wherein the cathode active material is a transition metal oxide comprising nickel, cobalt, and manganese, and when at 25 ℃ and 0.05 milliamps per square centimeter (mA/cm)2) When the positive electrode is discharged, the capacity of the positive electrode active material is in a range of 110 milliampere-hour/gram (mAh/g) to 220 mAh/g.
8. The cathode according to claim 1, wherein a ratio λ of an average particle diameter of the cathode active material to an average particle diameter of the first solid electrolyte is in a range of 3.3 to 8.
9. The positive electrode as claimed in claim 1, wherein the average particle diameter of the positive electrode active material is in a range of 5 μm to 20 μm.
10. The positive electrode as claimed in claim 1, wherein the average particle diameter of the positive electrode active material is in the range of 5 μm to 12 μm, and
the first solid electrolyte has an average particle diameter in a range of 1.5 to 4 μm,
wherein the amount of the positive electrode active material is in the range of 60 to 95 wt% based on the total weight of the positive electrode.
11. The positive electrode as claimed in claim 1, wherein the positive electrode active material is a nickel-based active material represented by formula 2:
formula 2
Lia(Ni1-x-y-zCoxMnyMz)O2
Wherein, in formula 2, M is an element selected from the group consisting of: boron (B), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr), and aluminum (Al); and is
A is more than or equal to 0.95 and less than or equal to 1.3, x is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, and z is more than or equal to 0 and less than 1.
12. The cathode of claim 1, wherein the first solid electrolyte is a sulfide solid electrolyte, an oxide solid electrolyte, or a combination thereof.
13. The positive electrode of claim 12, wherein the sulfide solid electrolyte is L i2S-P2S5L i wherein X is halogen2S-P2S5-LiX、Li2S-P2S5-Li2O、Li2S-P2S5-Li2O-LiI、Li2S-SiS2、Li2S-SiS2-LiI、Li2S-SiS2-LiBr、Li2S-SiS2-LiCl、Li2S-SiS2-B2S3-LiI、Li2S-SiS2-P2S5-LiI、Li2S-B2S3L i where m and n are positive numbers and Z is Ge, Zn, or Ga2S-P2S5-ZmSn、Li2S-GeS2、Li2S-SiS2-Li3PO4Wherein p and q are positive numbers and M1L i for P, Si, Ge, B, Al, Ga, or In2S-SiS2-LipM1OqWherein 0<x<L i of 27-xPS6-xClx) Wherein 0<x<L i of 27-xPS6-xBrxWherein 0<x<L i of 27-xPS6-xIxOr a combination thereof.
14. The positive electrode as claimed in claim 12, wherein the first solid electrolyte is 0 of<x<2 and 0. ltoreq. y<L i of 31+x+yAlxTi2-xSiyP3-yO12、BaTiO3Pb (Zr) wherein x is 0. ltoreq. x.ltoreq.1(1-x)Tix)O3Wherein x is not less than 0<1 and 0. ltoreq. y<Pb of 11-xLaxZr1-yTiyO3、Pb(Mg1/3Nb2/3)O3-PbTiO3、HfO2、SrTiO3、SnO2、CeO2、Na2O、MgO、NiO、CaO、BaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2、SiO2、SiC、Li3PO4Wherein 0<x<2 and 0<y<L i of 3xTiy(PO4)3Wherein 0<x<2、0<y<1 and 0<z<L i of 3xAlyTiz(PO4)3L i in which x is not less than 0 and not more than 1, y is not less than 0 and not more than 1, m is not less than 0 and not more than 1, and n is not less than 0 and not more than 11+x+y(Al(1-m)Gam)x(Ti(1-n)Gen)2-xSiyP3-yO12Wherein 0<x<2 and 0<y<L i of 3xLayTiO3Wherein 0<x<4、0<y<1、0<z<1 and 0<w<L i of 5xGeyPzSwWherein 0<x<4 and 0<y<L i of 2xNy、SiS2Wherein 0<x<3、0<y<2 and 0<z<L i of 4xSiySzWherein 0<x<3、0<y<3 and 0<z<L i of 7xPySz、Li2O、LiF、LiOH、Li2CO3、LiAlO2、Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2Ceramic, wherein M1L i being Te, Nb, or Zr and x being an integer of 1 to 103+xLa3M1 2O12) The garnet ceramic of (a), the compound of formula 5, or a combination thereof:
formula 5
(Li1-xM1x)7-yPS6-yM2y
Wherein, in formula 5, 0< x < 0.07 and 0< y < 2; m1 is Na, K, or a combination thereof; and is
M2 is F, Cl, Br, I, or a combination thereof.
15. The cathode of claim 1, wherein the solid electrolyte is a compound represented by formula 6, a compound represented by formula 7, or a combination thereof:
formula 6
Li5+xE3(Me1 zMe2 (2-z))Od
Wherein, in formula 6, E is a trivalent cation;
Me1and Me2Each independently is one selected from: trivalent cations, tetravalent cations, pentavalent cations, and hexavalent cations;
x is 0< x < 3, z is 0< z <2, and d is 0< d < 12; and is
O is optionally partially or fully replaced by a pentavalent anion, a hexavalent anion, a heptavalent anion, or a combination thereof;
formula 7
Li5+x+2y(DyE3-y)(Me1 zMe2 2-z)Od
Wherein, in formula 7, D is a monovalent cation or a divalent cation;
e is a trivalent cation;
Me1and Me2Each independently is a trivalent cation, a tetravalent cation, a pentavalent cation, or a hexavalent cation;
x +2y is 0< 3, y is 0< 0.5, z is 0< 2, and d is 0< 12; and is
O is optionally partially or fully replaced by a pentavalent anion.
16. The positive electrode according to claim 1, wherein the utilization rate of the positive electrode is 80% or more.
17. A positive electrode assembly comprising:
a positive electrode as claimed in any one of claims 1 to 16; and
a second solid electrolyte disposed on the positive electrode,
wherein the first solid electrolyte and the second solid electrolyte are the same as or different from each other.
18. The positive electrode assembly of claim 17, wherein the first solid electrolyte and the second solid electrolyte are each independently a sulfide solid electrolyte, an oxide solid electrolyte, or a combination thereof.
19. A solid-state secondary battery comprising: a positive electrode as claimed in any one of claims 1 to 16; a negative electrode; and a second solid electrolyte disposed between the positive electrode and the negative electrode, wherein the first solid electrolyte and the second solid electrolyte are the same as or different from each other.
20. The solid-state secondary battery according to claim 19, wherein the first solid electrolyte and the second solid electrolyte are each independently a sulfide solid electrolyte, an oxide solid electrolyte, or a combination thereof.
21. A method of preparing a positive electrode for a solid-state secondary battery, the method comprising:
providing a positive electrode active material;
providing a first solid electrolyte; and
contacting the positive electrode active material and the first solid electrolyte at a pressure in a range of 50 megapascals (MPa) to 600MPa to provide a positive electrode as claimed in any one of claims 1 to 16.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201962789812P | 2019-01-08 | 2019-01-08 | |
| US62/789,812 | 2019-01-08 | ||
| US201962823509P | 2019-03-25 | 2019-03-25 | |
| US62/823,509 | 2019-03-25 | ||
| US16/459,896 US11108035B2 (en) | 2019-01-08 | 2019-07-02 | Solid-state positive electrode, method of manufacture thereof, and battery including the electrode |
| US16/459,896 | 2019-07-02 | ||
| KR1020190136947A KR20200086211A (en) | 2019-01-08 | 2019-10-30 | Positive electrode for solid state secondary battery, preparing method thereof, and positive electrode assembly for solid state secondary battery and solid state secondary battery including the same |
| KR10-2019-0136947 | 2019-10-30 | ||
| KR1020200001758A KR20200086227A (en) | 2019-01-08 | 2020-01-07 | Positive electrode for solid state secondary battery, preparing method thereof, and positive electrode assembly for solid state secondary battery and solid state secondary battery including the same |
| KR10-2020-0001758 | 2020-01-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111416115A true CN111416115A (en) | 2020-07-14 |
Family
ID=71493968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010017090.0A Pending CN111416115A (en) | 2019-01-08 | 2020-01-08 | Positive electrode for solid secondary battery, method for producing same, positive electrode assembly, and solid secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111416115A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113140730A (en) * | 2021-03-26 | 2021-07-20 | 万向一二三股份公司 | High-nickel ternary lithium ion battery |
| CN114520317A (en) * | 2021-12-28 | 2022-05-20 | 国联汽车动力电池研究院有限责任公司 | High-compaction composite positive electrode material for solid-state battery and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11111266A (en) * | 1997-09-30 | 1999-04-23 | Yuasa Corp | High polymer electrolyte secondary battery |
| US20130040206A1 (en) * | 2010-02-26 | 2013-02-14 | Zeon Corporation | All solid-state secondary battery and a production method of an all solid-state secondary battery |
| JP2015005398A (en) * | 2013-06-20 | 2015-01-08 | トヨタ自動車株式会社 | Positive electrode for all-solid lithium ion battery |
| US20170092987A1 (en) * | 2015-09-24 | 2017-03-30 | Toyota Jidosha Kabushiki Kaisha | Method of manufacturing electrode laminate and method of manufacturing all-solid-state battery |
| CN107093764A (en) * | 2016-02-18 | 2017-08-25 | 丰田自动车株式会社 | Anode mixture, positive pole and all-solid-state lithium-ion secondary battery and their manufacture method |
-
2020
- 2020-01-08 CN CN202010017090.0A patent/CN111416115A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11111266A (en) * | 1997-09-30 | 1999-04-23 | Yuasa Corp | High polymer electrolyte secondary battery |
| US20130040206A1 (en) * | 2010-02-26 | 2013-02-14 | Zeon Corporation | All solid-state secondary battery and a production method of an all solid-state secondary battery |
| JP2015005398A (en) * | 2013-06-20 | 2015-01-08 | トヨタ自動車株式会社 | Positive electrode for all-solid lithium ion battery |
| US20170092987A1 (en) * | 2015-09-24 | 2017-03-30 | Toyota Jidosha Kabushiki Kaisha | Method of manufacturing electrode laminate and method of manufacturing all-solid-state battery |
| CN107093764A (en) * | 2016-02-18 | 2017-08-25 | 丰田自动车株式会社 | Anode mixture, positive pole and all-solid-state lithium-ion secondary battery and their manufacture method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113140730A (en) * | 2021-03-26 | 2021-07-20 | 万向一二三股份公司 | High-nickel ternary lithium ion battery |
| CN114520317A (en) * | 2021-12-28 | 2022-05-20 | 国联汽车动力电池研究院有限责任公司 | High-compaction composite positive electrode material for solid-state battery and preparation method and application thereof |
| CN114520317B (en) * | 2021-12-28 | 2023-08-15 | 国联汽车动力电池研究院有限责任公司 | High-compaction composite positive electrode material for solid-state battery and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11764407B2 (en) | All-solid-state secondary battery including anode active material alloyable with lithium and method of charging the same | |
| EP2437337B1 (en) | Cathode, method of preparing the same, and lithium battery including the cathode | |
| US11682791B2 (en) | Solid electrolyte, electrochemical battery including the solid electrolyte, and method of preparing the solid electrolyte | |
| CN112786948A (en) | All-solid-state secondary battery | |
| US20210336269A1 (en) | All-SOLID-STATE SECONDARY BATTERY | |
| US20210135280A1 (en) | Solid ion conductor compound, solid electrolyte including solid ion conductor compound, electrochemical cell including solid ion conductor compound, and method of preparing solid ion conductor compound | |
| WO2020174868A1 (en) | Positive electrode material, and battery | |
| JP7130911B2 (en) | Positive electrode for all-solid secondary battery, and all-solid secondary battery including the same | |
| KR20210117002A (en) | Positive active material for all solid secondary battery, and all solid secondary battery including the same | |
| KR20220014809A (en) | Positive electrode active material layer, preparing method thereof, positive electrode comprising the positive electrode active material layer, and lithium battery including the same | |
| US20130011731A1 (en) | Cathode slurry composition, cathode prepared from the same, and lithium battery comprising the cathode | |
| EP3680959B1 (en) | Positive electrode for solid-state secondary battery, method of preparing the same, positive electrode assembly for solid-state secondary battery including the same, and solid-state secondary battery including the same | |
| CN111416115A (en) | Positive electrode for solid secondary battery, method for producing same, positive electrode assembly, and solid secondary battery | |
| JP7106702B2 (en) | Positive electrode for all-solid secondary battery, and all-solid secondary battery including the same | |
| CN113381017A (en) | All-solid-state secondary battery | |
| US20220199995A1 (en) | Anode material for all-solid secondary battery, anode layer and all-solid secondary battery including the same, and manufacturing method thereof | |
| KR20190125174A (en) | Fluoride ion battery | |
| JP7284225B2 (en) | Sulfide-based solid electrolyte for all-solid secondary battery, method for producing the same, and all-solid secondary battery including the same | |
| JP2023548332A (en) | Batteries with solid electrolyte multilayers | |
| CN113614948A (en) | Positive electrode material and battery | |
| US20230170524A1 (en) | Solid ion conductor compound, electrochemical cell comprising the same, and preparation method thereof | |
| WO2022259820A1 (en) | Coated positive electrode active substance, positive electrode material, and battery | |
| US20220173431A1 (en) | All-solid-state battery | |
| WO2022254796A1 (en) | Electrode material and battery | |
| WO2021215215A1 (en) | Battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |