EP3766119A1 - Electrolyte solide pour dispositifs electrochimiques - Google Patents
Electrolyte solide pour dispositifs electrochimiquesInfo
- Publication number
- EP3766119A1 EP3766119A1 EP19728502.6A EP19728502A EP3766119A1 EP 3766119 A1 EP3766119 A1 EP 3766119A1 EP 19728502 A EP19728502 A EP 19728502A EP 3766119 A1 EP3766119 A1 EP 3766119A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- electrolyte
- battery
- deposited
- anode
- 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 description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 144
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 238000000151 deposition Methods 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 52
- 239000000725 suspension Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000003618 dip coating Methods 0.000 claims abstract description 20
- 238000001962 electrophoresis Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- 238000007906 compression Methods 0.000 claims abstract description 10
- 230000006835 compression Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims description 89
- 238000000231 atomic layer deposition Methods 0.000 claims description 56
- 229920000052 poly(p-xylylene) Polymers 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 48
- 238000005538 encapsulation Methods 0.000 claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 239000004642 Polyimide Substances 0.000 claims description 31
- 229920001721 polyimide Polymers 0.000 claims description 31
- 239000012212 insulator Substances 0.000 claims description 29
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052718 tin Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 238000000280 densification Methods 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- -1 supercapacitors Substances 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 11
- 239000012777 electrically insulating material Substances 0.000 claims description 10
- 239000004952 Polyamide Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000003990 capacitor Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 5
- 239000007771 core particle Substances 0.000 claims description 5
- 230000006378 damage Effects 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 362
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 51
- 229910052782 aluminium Inorganic materials 0.000 description 35
- 238000000576 coating method Methods 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 30
- 239000012071 phase Substances 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 29
- 239000002608 ionic liquid Substances 0.000 description 29
- 230000008021 deposition Effects 0.000 description 28
- 239000000243 solution Substances 0.000 description 23
- 229910052727 yttrium Inorganic materials 0.000 description 23
- 210000004027 cell Anatomy 0.000 description 22
- 238000000224 chemical solution deposition Methods 0.000 description 20
- 229910003002 lithium salt Inorganic materials 0.000 description 20
- 159000000002 lithium salts Chemical class 0.000 description 20
- 239000010936 titanium Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
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- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 229910052733 gallium Inorganic materials 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- 239000010416 ion conductor Substances 0.000 description 10
- 239000011244 liquid electrolyte Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000001652 electrophoretic deposition Methods 0.000 description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- 238000007306 functionalization reaction Methods 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- 230000003071 parasitic effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 230000032258 transport Effects 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000007596 consolidation process Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007766 curtain coating Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
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- 229910052712 strontium Inorganic materials 0.000 description 3
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- 239000010409 thin film Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 2
- 241001175904 Labeo bata Species 0.000 description 2
- 101000690484 Leptodactylus fallax Aggression-stimulating peptide Proteins 0.000 description 2
- 229910013376 LiBSO Inorganic materials 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910012258 LiPO Inorganic materials 0.000 description 2
- 229910012305 LiPON Inorganic materials 0.000 description 2
- 229910012360 LiSiPON Inorganic materials 0.000 description 2
- 229910013439 LiZr Inorganic materials 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
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- 239000002041 carbon nanotube Substances 0.000 description 2
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- 238000004320 controlled atmosphere Methods 0.000 description 2
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- 210000001787 dendrite Anatomy 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 230000002427 irreversible effect Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 1
- YQFWGCSKGJMGHE-UHFFFAOYSA-N 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1 YQFWGCSKGJMGHE-UHFFFAOYSA-N 0.000 description 1
- VRBFTYUMFJWSJY-UHFFFAOYSA-N 28804-46-8 Chemical compound ClC1CC(C=C2)=CC=C2C(Cl)CC2=CC=C1C=C2 VRBFTYUMFJWSJY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910018122 Li 3-x M Inorganic materials 0.000 description 1
- 229910013189 LiBON Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910013086 LiNiPO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012311 LiPONB Inorganic materials 0.000 description 1
- 229910012428 LiSON Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- WTQZCJZGAXKVEY-UHFFFAOYSA-N S=O.[Li].[Ti] Chemical class S=O.[Li].[Ti] WTQZCJZGAXKVEY-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910020328 SiSn Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910005790 SnSiO Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
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- 238000005275 alloying Methods 0.000 description 1
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- SESRATMNYRWUTR-UHFFFAOYSA-N sulfinyltitanium Chemical class [Ti].S=O SESRATMNYRWUTR-UHFFFAOYSA-N 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
-
- 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
- H01M2300/0025—Organic electrolyte
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
Definitions
- the invention relates to the field of electrochemistry, and more particularly to fully solid lithium ion batteries. It relates more specifically solid electrolytes and more particularly the thin-layer electrolytes used in these electrochemical systems.
- the invention also relates to a process for preparing such an electrolyte, preferably in a thin layer, which uses nanoparticles of solid electrolyte materials, preferably of lithium phosphate on which PEO molecules have been grafted, and the electrolytes thus obtained.
- the invention also relates to a method of manufacturing an electrochemical device comprising at least one of these electrolytes, and the devices thus obtained.
- a lithium ion battery is an electrochemical component that stores electrical energy. In general, it is composed of one or more elementary cells, and each cell comprises two electrodes with opposite polarity and an electrolyte. Various types of electrolytes can be used in lithium ion secondary batteries.
- a cell may comprise two electrodes separated by a polymeric porous membrane (also called “separator”) impregnated with a liquid electrolyte containing a lithium salt.
- patent application JP 2002-042792 describes a method of electrophoretically depositing a solid electrolyte on an electrode of a battery.
- the electrolytes described are essentially polymeric membranes such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride whose pores are impregnated with a lithium salt such as LiPF 6 .
- the size of the particles deposited by electrophoresis should preferably be less than 1 ⁇ m, and the layer formed preferably has a thickness of less than 10 ⁇ m.
- the liquid electrolyte migrates both into the porosities contained in the membrane and towards the electrodes, and thus ensures the ionic conduction between the electrodes.
- these polymer membranes impregnated with a liquid electrolyte have a lower ionic conductivity than the liquid electrolyte used. This effect can be compensated for by reducing the thickness of the membranes.
- these polymeric membranes are mechanically fragile and can have their electrical insulation properties altered by the effect of strong electric fields as is the case in batteries charged with electrolyte films of very thin thickness, or under effect of mechanical and especially vibratory stresses.
- These polymeric membranes tend to break during charge and discharge cycles, causing anode and cathode particles to detach; this can cause a short circuit between the two positive and negative electrodes, which can lead to dielectric breakdown. This risk is also accentuated in batteries using porous electrodes.
- ceramic fillers in the polymer matrix makes it possible to improve the morphological and electrochemical properties of the polymeric electrolytes; these ceramic fillers can be active (such as Li 2 N, UAI 2 O 3 ), in which case they participate in the lithium ion transport process, or be passive (such as Al 2 O 3 , SiO 2 , MgO), in which case they do not participate in the process of transporting lithium ions.
- the first drawback is that it degrades the number of electrolyte transport: only solid electrolytes without lithium salts or liquids Ionic acids (such as lithiated phosphates) have a transport number of 1.
- the second drawback is that the chemical stability of high-potential PEO is less good when the PEO matrix is impregnated with lithium salts and / or ionic liquids than when it contains nanoparticles of solid electrolyte (see Zhang's publication cited here). -above). In these electrolytes, the conduction is essentially provided by the nanoparticles; the amorphous phases of the PEO promote the transfer of lithium ions to the interfaces, on the one hand between the particles and on the other hand between the particles and the electrodes.
- the present invention aims to remedy at least in part these disadvantages of the prior art.
- the problem that the present invention seeks to solve is to provide electrolytes that are safe, can be used in a thin layer, have a high ionic conductivity and a transport number close to 1, a stable mechanical structure and a long life.
- Another problem that the present invention seeks to solve is to provide a method of manufacturing such an electrolyte that is simple, safe, fast, easy to implement, easy to industrialize and inexpensive.
- Another object of the invention is to provide electrolytes for batteries capable of operating reliably and without risk of fire.
- Another object of the invention is to provide a rigid structure battery having a high power density capable of mechanically withstanding shocks and vibrations.
- Another object of the invention is to provide a method for manufacturing an electronic, electrical or electrotechnical device such as a battery, a capacitor, a supercapacitor, a photovoltaic cell comprising an electrolyte according to the invention.
- Another object of the invention is to provide devices such as batteries, lithium ion battery cells, capacitors, supercapacitors, photovoltaic cells having increased reliability, having a long life and can be encapsulated by coatings deposited by the Atomic Layer Deposition (ALD) technique, at elevated temperature and under reduced pressure.
- ALD Atomic Layer Deposition
- a second object of the invention is a method for manufacturing an electrolyte, preferably a solid electrolyte, preferably in a thin layer, for a lithium ion battery or supercapacitor, deposited on an electrode, comprising the steps of: a. supplying a conductive substrate, previously covered with a layer of a material that can serve as an electrode (“electrode layer”),
- an electrolyte layer preferably by electrophoresis or dip-coating, from a suspension of core-shell particles comprising as a core a particle of a material which can serve as an electrolyte and / or electronic insulation, on which is grafted a bark comprising PEO;
- the electrolyte according to the invention can be obtained from the deposition on said electrode layer of an electrolyte layer, preferably by electrophoresis or dip-coating, from a suspension comprising core particles.
- -bark comprising as a core, a particle of a material which can serve as an electrolyte, on which is grafted a bark comprising PEO, and / or comprising core-bark particles comprising as a core, a particle of a material which can serve as electronic insulation , on which is grafted a bark comprising PEO.
- the average size D 5 o of the primary core particles is less than 100 nm, preferably less than 50 nm and even more preferably less than or equal to 30 nm.
- the primary core particles are obtained by hydrothermal or solvothermal synthesis.
- the thickness of the bark of the core-shell particles is between 1 nm and 100 nm.
- the electrolyte layer obtained in step c) or d) has a thickness less than 10 ⁇ m, preferably about 6 ⁇ m and even more preferably about 3 ⁇ m.
- the PEO has a weight average molecular weight of less than 7000 g / mol, preferably about 5000 g / mol.
- the dry extract of the suspension of core-bark particles used in step b) is less than 30% by mass.
- the process according to the invention can be used for the manufacture of electrolytes, preferably solid, preferably in thin layers, in electronic, electrical or electrotechnical devices, and preferably in devices selected from the group formed by: batteries , capacitors, supercapacitors, capacitors, resistors, inductors, transistors.
- Another subject of the invention is an electrolyte that can be obtained by the process according to the invention, preferably a solid electrolyte, preferably a thin-layer electrolyte.
- the electrolyte according to the invention preferably in a thin layer, comprising a solid electrolyte and PEO, has a solid electrolyte / PEO volume ratio greater than 35%, preferably greater than 50%, preferably greater than 60%. and even more preferably greater than 70%.
- the electrolyte according to the invention preferably in a thin layer, has a porosity of less than 20%, preferably less than 15%, even more preferably less than 10%.
- Another subject of the invention is an electrochemical device comprising at least one electrolyte, preferably a solid electrolyte, preferably a layered electrolyte. thin, according to the invention, preferably a lithium ion battery or a supercapacitor.
- Another subject of the invention is a method for manufacturing a lithium ion battery implementing the method according to the invention, and comprising the steps of:
- step iii Deposition of an electrolyte layer, preferably by electrophoresis or dip-coating, from a suspension of core-shell particles obtained in step ii), on the cathode layer, and / or anode obtained in step i), to obtain a first and / or a second intermediate structure, iv. Drying of the layer thus obtained in step iii), preferably under a stream of air,
- the method of manufacturing a lithium ion battery according to the invention includes a step of impregnation of the battery obtained in step vi) by a lithium ion carrier phase leading to obtaining an impregnated battery.
- said material that can serve as an electronic insulator is preferably selected from I ⁇ I2O3, Si0 2 , Zr0 2 .
- the cathode is a dense electrode
- a dense electrode coated with ALD or a chemical solution (CSD) of an electronically insulating layer preferably an electronically insulating and ionically conductive layer
- an electronically insulating layer preferably an electronically insulating and ionically conductive layer
- anode is a dense electrode
- a dense electrode coated with ALD or a chemical solution (CSD) of an electronically insulating layer preferably an electronically insulating and ionically conductive layer
- an electronically insulating layer preferably an electronically insulating and ionically conductive layer
- CSD chemical solution
- - is deposited successively, alternately, on the battery: at least a first layer of parylene and / or polyimide on said battery,
- At least one second layer composed of an electrically insulating material by atomic layer deposition ALD (Atomic Layer Deposition) on said first layer of parylene and / or polyimide,
- ALD atomic layer deposition
- a layer for protecting the battery against mechanical damage to the battery preferably silicone, epoxy resin or parylene, or polyimide forming, a system encapsulation of the battery
- the battery thus encapsulated is cut off according to two section planes to expose each of the cutting planes of the anode and cathode connections of the battery, so that the encapsulation system covers four of the six faces of said battery, preferably continuously,
- the battery is successively deposited, alternately, an encapsulation system formed by a succession of layers, namely a sequence, preferably z sequences, comprising:
- a first covering layer preferably chosen from parylene, type F parylene, polyimide, epoxy resins, silicone, polyamide and / or a mixture thereof, deposited on the assembled stack,
- a second covering layer composed of an electrically insulating material deposited by deposit of atomic layers on said first cover layer
- This sequence can be repeated z times with z> 1, a final layer is deposited on this succession of layers of a material chosen from epoxy resin, polyethylene naphthalate (PEN), polyimide, polyamide, polyurethane silicone, sol-gel silica or organic silica,
- a material chosen from epoxy resin, polyethylene naphthalate (PEN), polyimide, polyamide, polyurethane silicone, sol-gel silica or organic silica,
- the battery thus encapsulated is cut off according to two section planes to expose each of the cutting planes of the anode and cathode connections of the battery, so that the encapsulation system covers four of the six faces of said battery, preferably continuously,
- the encapsulated battery thus cut is impregnated with a phase carrying lithium ions, in particular when this battery comprises at least one porous electrode,
- a first layer of a graphite-loaded material preferably a graphite-filled epoxy resin
- a second layer comprising metallic copper obtained from an ink loaded with copper nanoparticles deposited on the first layer
- the layers obtained are thermally treated, preferably by infrared flash lamp, so as to obtain a covering of the cathodic and anodic connections by a layer of metallic copper,
- this layer of metallic copper is deposited successively on and around:
- a first layer of a tin-zinc alloy deposited preferably by dipping in a molten tin-zinc bath, in order to ensure the tightness of the battery at a lower cost
- the anode and cathode connections are on the opposite sides of the stack.
- Another object of the invention is a lithium ion battery obtainable by this method.
- Another object of the invention is a lithium ion battery comprising an electrolyte according to the invention.
- FIG. 1 is a diagrammatic view of a cutaway front view of a battery comprising an electrolyte according to the invention and showing the structure of the battery comprising, for illustrative purposes, an assembly of elementary cells covered by a battery system. encapsulation and terminations.
- the size of a particle is defined by its largest dimension.
- nanoparticle is meant any particle or object of nanometric size D 5 o having at least one of its dimensions less than or equal to 100 nm.
- an electronically insulating material or layer preferably an electronically insulating and ionically conductive layer is a material or a layer whose electrical resistivity (resistance to electron passage) is greater than 10 5 W-cm.
- thin layer is meant any film of thickness less than 10 .mu.m.
- mesoporous materials any solid which has within its structure so-called “mesopore” pores having an intermediate size between that of micropores (width less than 2 nm) and that of macropores (width greater than 50 nm), namely a size between 2 nm and 50 nm.
- This terminology corresponds to that adopted by IUPAC (International Union for Pure and Applied Chemistry), which refers to the skilled person.
- IUPAC International Union for Pure and Applied Chemistry
- mesoporous layer means a layer which has mesopores.
- nanoparticles of electrolyte or electronic insulator are supplied, preferably in the form of a suspension in a liquid phase.
- the electrolyte nanoparticles can be prepared by nanomilling / dispersion of a solid electrolyte powder (or electronic insulator) or by hydrothermal synthesis or by solvothermal synthesis or by precipitation.
- a method for obtaining primary nanoparticles very homogeneous size monodisperse.
- the solvothermal pathway for example hydrothermal, is preferred, which leads to nanoparticles having a very homogeneous size, good crystallinity and purity, whereas nanomilling tends to deteriorate the solid nanoparticles.
- the synthesis of nanoparticles by precipitation also makes it possible to obtain primary nanoparticles of very homogeneous size, of good crystallinity and purity.
- the nanoparticles of electrolyte or electronic insulator can then be functionalized with organic molecules in a liquid phase, according to methods known to those skilled in the art.
- the functionalization consists in grafting on the surface of the nanoparticles a molecule having a structure of the Q-Z type in which Q is a function ensuring the adhesion of the molecule to the surface, and Z is a PEO group.
- a complexing function of the surface cations of the nanoparticles can be used such as the phosphate or phosphonate function.
- the nanoparticles of electrolyte or electronic insulator are functionalized by a derivative of PEO type where X represents an alkyl chain or a hydrogen atom,
- n is between 40 and 10,000 (preferably between 50 and 200),
- n is from 0 to 10
- Q ' is an embodiment of Q and represents a group selected from the group consisting of:
- R represents an alkyl chain or a hydrogen atom
- R ' represents a methyl group or an ethyl group
- x is between 1 and 5
- x' is between 1 and 5.
- the nanoparticles of electrolyte or electronic insulation are functionalized with methoxy-PEO-phosphonate
- n is between 40 and 10,000 and preferably between 50 and 200.
- a solution of QZ (or Q'-Z, where appropriate) is added to a colloidal suspension of nanoparticles of electrolyte or of electronic insulator so as to obtain a molar ratio between Q (which comprises here Q ') and the set of cations present in the nanoparticles of electrolyte or electronic insulator (here abbreviated as "NP-E") of between 1 and 0.01, preferably between 0.1 and 0.02.
- the functionalization of the nanoparticles of electrolyte or of electronic insulator by the QZ molecule risks to induce a steric hindrance such that the electrolyte particles can not be fully functionalized; it also depends on the particle size.
- the QZ molecule may not be in sufficient quantity to ensure sufficient conductivity of the lithium ions; it also depends on the particle size. Using a greater amount of QZ during functionalization would result in unnecessary QZ consumption.
- the material that can serve as an electronic insulator is preferably chosen from I ⁇ I 2 O 3 , SiO 2 , ZrO 2 , and / or a material selected from the group formed by the electrolyte materials hereinafter.
- electrolyte nanoparticles are chosen from:
- ⁇ A 1 is a cation of oxidation + II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and or
- ⁇ A 2 represents a cation of degree of oxidation 111, preferably Al, Fe, Cr, Ga, Ti, La; and or
- ⁇ (TO 4) is an anion wherein T is an atom with an oxidation number + IV, located at the center of a tetrahedron formed by the oxygen atoms, and wherein T0 4 advantageously is the anion silicate or zirconate , knowing that all or part of the elements T of a degree of oxidation + IV can be replaced by atoms of a degree of oxidation +111 or + V, such as Al, Fe, As, V, Nb, In , Ta;
- d is between 2 and 10, preferably between 3 and 9, and even more preferably between 4 and 8;
- x is between 2.6 and 3.4 (preferably between 2.8 and 3.2);
- y is from 1.7 to 2.3 (preferably from 1.9 to 2.1) and
- z is from 2.9 to 3.1;
- the oxynitrides preferably chosen from Li 3 PO 4 -xN 2x / 3 , Li 4 SiO 4- x N 2 x / 3, Li 4 Ge0 4 -XN 2x / 3 with 0 ⁇ x ⁇ 4 or Li 3 B0 3 -xN 2x / 3 with 0 ⁇ x ⁇ 3;
- LiPON lithium oxynitride and phosphorus
- Li x PO y N z Li x PO y N z with x ⁇ 2.8 and 2y + 3z ⁇ 7.8 and 0.16 ⁇ z ⁇ 0 , 4, and in particular Ü 2,9PO 3,3 N 0, 46
- LiPON lithium oxynitrides
- LIBON lithium oxynitride materials
- LiSiPON lithiated compounds based on lithium oxynitride, phosphorus and silicon called “LiSiPON", and in particular Lii 9 Sio 28Pi OOi i Ni 0 ;
- lithium oxynitrides of LiBON, LiBSO, LiSiPON, LiSON, thio-LiSiCON, LiPONB (or B, P and S respectively represent boron, phosphorus and sulfur);
- o silicates preferably selected from L ⁇ S ⁇ Os, Li 2 SI03, L ⁇ S ⁇ Oe, LiAISi0 4, Li 4 Si0 4, LÎAISÎ206!
- solid electrolytes of anti-perovskite type chosen from: Li 3 OA with a halide or a mixture of halides, preferably at least one of F, Cl, Br, I or a mixture of two or three or four of these elements; Li (3-x) M x / 20A with 0 ⁇ x ⁇ 3, M a divalent metal, preferably at least one of Mg, Ca, Ba, Sr or a mixture of two or three or four of these elements, a halide or a mixture of halides, preferably at least one of F, Cl, Br, I or a mixture of two or three or four of these elements; ⁇ (3 -c) c M 3 / 30A with 0 ⁇ x ⁇ 3, M 3 a trivalent metal, A halide or mixture of halides, preferably at least one element selected from F, mixture of two or three or four of these elements; or LiCOX z YY halides as mentioned above in connection with
- electrolyte layers obtained from electrolyte nanoparticles functionalized with PEO the electrolyte nanoparticles of which are chosen from:
- ⁇ A 1 is a cation of oxidation + II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and or
- ⁇ A 2 represents a cation with an oxidation number + III, preferably Al, Fe, Cr, Ga, Ti, La; and or
- ⁇ (T0) represents an anion wherein T is an atom with an oxidation number + IV, located at the center of a tetrahedron formed by the oxygen atoms, and wherein T0 4 advantageously is the anion silicate or zirconate, knowing that all or part of the elements T of a degree of oxidation + IV can be replaced by atoms of a degree of oxidation + III or + V, such as Al, Fe, As, V, Nb, In, Ta; ⁇ knowing that: d is between 2 and 10, preferably between 3 and 9, and even more preferably between 4 and 8; x is between 2.6 and 3.4 (preferably between 2.8 and 3.2); y is from 1.7 to 2.3 (preferably from 1.9 to 2.1) and z is from 2.9 to 3.1;
- M 3 Cr, V, Ca, B, Mg, Bi and / or Mo
- M Sc, Sn, Zr, Hf, Se or Si, or a mixture of these compounds
- a colloidal suspension of electrolyte nanoparticles at a mass concentration of between 0.1% and 50%, preferably between 5% and 25% and even more preferentially at 10% is used to carry out the functionalization of the electrolyte particles.
- the electrolyte nanoparticles are dispersed in a liquid phase such as water or ethanol. This reaction can be carried out in any suitable solvent for solubilizing the QZ molecule.
- the functionalization conditions can be optimized, in particular by adjusting the temperature and the duration of the reaction, and the solvent used.
- the reaction medium After adding a solution of QZ to a colloidal suspension of electrolyte nanoparticles, the reaction medium is left stirring for 0 h to 24 hours (preferably for 5 minutes to 12 hours, even more preferably for 0.5 hours to 2 hours). hours), so that at least a portion, preferably all of the QZ molecules can be grafted onto the surface of the electrolyte nanoparticles.
- the functionalization can be carried out under heating, preferably at a temperature between 20 ° C and 100 ° C. The temperature of the reaction medium must be adapted to the choice of the functionalizing molecule Q-Z.
- These functionalized nanoparticles therefore have a core ("core") of electrolyte material and PEO bark.
- the thickness of the bark may typically be between 1 nm and 100 nm; this thickness can be determined by transmission electron microscopy, typically after labeling the polymer with ruthenium oxide (RuO 4 ).
- the nanoparticles thus functionalized are then purified by cycles of centrifugations and successive redispersions and / or by tangential filtration.
- the colloidal suspension of functionalized electrolyte nanoparticles is centrifuged to separate the functionalized particles from the unreacted Q-Z molecules present in the supernatant. After centrifugation, the supernatant is removed.
- the pellet comprising the functionalized particles is redispersed in the solvent.
- the pellet comprising the functionalized particles is redispersed in an amount of solvent making it possible to reach the desired solids content. This redispersion can be carried out by any means, in particular by the use of an ultrasonic bath or else with magnetic and / or manual stirring.
- cycles of successive centrifugations and redispersions can be carried out so as to eliminate unreacted Q-Z molecules.
- the suspension can be reconcentrated until the desired solids content is obtained, by any appropriate means.
- the dry extract of a suspension of electrolyte nanoparticles functionalized with PEO comprises more than 40% (by volume) of solid electrolyte material, preferably more than 60% and even more preferentially more than 70% of material. solid electrolyte.
- the solid electrolyte can be deposited electrophoretically, by the coating process, by dipping (called “dip-coating” in English), or by other deposition techniques known to the human being. a profession allowing the use of a suspension of electrolyte nanoparticles or electronic insulators functionalized with PEO.
- the dry extract of the suspension of electrolyte nanoparticles or PEO functionalized electronic insulators used to deposit an electrolyte layer electrophoretically by dip-coating or by other known deposition techniques of the electrolyte.
- one skilled in the art according to the invention is less than 30% by weight; such a suspension is sufficiently stable during the deposit.
- the solid electrolyte is deposited electrophoretically, or dip-coating.
- the electrolyte layer is deposited on an anode layer 12 and / or a cathode layer 22 themselves formed on a conductive substrate 11, 21 by a suitable method, and / or directly on a sufficiently conductive substrate 11, 21 .
- This conductive or sufficiently conductive substrate 11, 21 serves as a current collector within the batteries employing an electrolyte according to the invention.
- This substrate may be metallic, for example a metal foil, or a metallized polymeric or non-metallic foil (i.e. coated with a metal layer).
- the substrate is preferably selected from strips of titanium, copper, nickel or stainless steel.
- the metal sheet may be coated with a layer of noble metal, in particular chosen from gold, platinum, palladium, titanium or alloys containing predominantly at least one or more of these metals, or a layer of material ITO type conductor (which has the advantage of also acting as a diffusion barrier).
- a layer of noble metal in particular chosen from gold, platinum, palladium, titanium or alloys containing predominantly at least one or more of these metals, or a layer of material ITO type conductor (which has the advantage of also acting as a diffusion barrier).
- the liquid phase carrying lithium ions which impregnates the porous electrode is in direct contact with the current collector.
- this liquid phase carrying lithium ions is in contact with the metal substrate and polarized at very anode potentials for the cathode and very cathodic for the anode, these liquid phases carrying lithium ions are likely to induce a dissolution of the current collector. These parasitic reactions can degrade the life of the battery and speed up its self-discharge.
- aluminum current collectors are used at the cathode, in all lithium ion batteries. Aluminum has the characteristic of being anodized with very anodic potentials, and the oxide layer thus formed on its surface protects it from dissolution.
- the aluminum has a melting temperature close to 60053 and can not be used for the manufacture of batteries comprising at least one porous electrode.
- the consolidation treatments of the fully solid electrodes would lead to melt the current collector.
- a titanium strip is advantageously used as a current collector at the cathode.
- the titanium strip will, like aluminum, anodize and its oxide layer will prevent any parasitic reactions dissolution of titanium in contact with the liquid phase carrier of lithium ions.
- fully solid electrodes according to the invention can be produced directly on this type of strip.
- Stainless steel can also be used as a current collector, especially when it contains titanium or aluminum as an alloying element, or when it has a thin layer of protective oxide on the surface.
- substrates serving as current collector may be used such as less noble metal strips coated with a protective coating, to avoid the possible dissolution of these strips induced by the presence of electrolytes on contact.
- These less noble metal strips may be copper strips, nickel or strip of metal alloys such as stainless steel strips, Fe-Ni alloy strips, Be-Ni-Cr alloy, alloy Ni-Cr or Ni-Ti alloy.
- the coating that can be used to protect substrates serving as current collectors can be of different kinds. It can be a: i. thin layer obtained by sol-gel process of the same material as that of the electrode. The absence of porosity in this film makes it possible to avoid contact between a lithium ion po ⁇ tering liquid phase and the metal current collector, ii. thin layer obtained by vacuum deposition, in particular by physical vapor deposition (or PVD) or by chemical vapor deposition (CVD), of the same material as of the electrode,
- thin metal layer dense, flawless, such as a thin metal layer of gold, titanium, platinum, palladium, tungsten or molybdenum.
- This layer can in particular be made by electrochemistry, PVD, CVD, evaporation, ALD,
- ALD ALD, PVD, CVD or inking of a sol-gel solution making it possible to obtain, after thermal treatment, an inorganic phase doped with carbon to make it conductive,
- v. conducting oxide layer such as a layer of ITO (indium-tin oxide) only deposited on the cathode substrate because the oxides are reduced to low potentials
- conductive nitride layer such as a layer of TiN only deposited on the cathode substrate because the nitrides insert the lithium at low potentials.
- the coating that can be used to protect the substrates serving as current collectors must be electronically conductive so as not to interfere with the operation of the electrode subsequently deposited on this coating, making it too resistive.
- the maximum dissolution currents measured on the substrates, at the operating potentials of the electrodes, expressed in mA / cm 2 must be 1000 times lower than the surface capacities. electrodes expressed in pAh / cm 2 .
- anode and cathode layers can be performed on this type of substrate serving as a current collector by any appropriate means.
- These anode and cathode layers can be dense, ie have a volume porosity of less than 20%. They can also be porous, and in this case it is preferred that they exhibit a interconnected network of open porosity; this porosity is preferably a mesoporosity, with pores with a mean diameter of between 2 nm and 50 nm.
- the process according to the invention can use the electrophoresis of nanoparticle suspensions as a technique for depositing the porous layers.
- the process of depositing layers from a suspension of nanoparticles is known per se (see, for example, EP 2 774 208 B1).
- the electrophoretic deposition of functionalized particles by PEO is done by the application of an electric field between the conductive substrate on which the deposit is made, and a counter-electrode, for putting the charged particles of the colloidal suspension in motion, and deposit them on the substrate.
- the electrophoretic deposition rate is a function of the applied electric field and the electrophoretic mobility of the particles of the suspension. It can be very high. For example, for an applied voltage of 200 V, the deposition rate can be up to about 10 pm / min.
- the inventor has found that this technique makes it possible to deposit very homogeneous layers over very large areas (provided that the particle concentration and the electric field are homogeneous on the surface of the substrate).
- the electrophoresis deposition can be implemented in a batch process (static) or in a continuous process.
- the electrolyte layer is deposited on an anode layer 12 and / or a cathode layer 22 themselves formed on a conductive substrate 11, 21 by a suitable method, and / or directly on a sufficiently conductive substrate.
- the substrate serving as a current collector within the batteries employing porous electrodes according to the invention is preferably chosen from strips made of titanium, copper, stainless steel or nickel.
- a conductive substrate may be a metal substrate, such as a stainless steel strip, of a thickness which may be, for example, 5 ⁇ m, or a polymer strip having an electrically conductive surface layer.
- a stainless steel sheet with a thickness of 5 ⁇ m can be used.
- the metal foil may be coated with a layer of noble metal, in particular chosen from gold, platinum, palladium, titanium or alloys containing predominantly at least one or several of these metals, or a layer of conductive material of the ITO type (which has the advantage of also acting as a diffusion barrier). Deposition of the anode and cathode layers can be performed on this type of conductive substrate by any suitable means.
- These anode and cathode layers can be dense, ie have a volume porosity of less than 20%. They may also be porous, and in this case it is preferred that they have an interconnected open porosity network; this porosity is preferably a mesoporosity, with pores with a mean diameter of between 2 nm and 50 nm.
- a stabilized power supply makes it possible to apply a voltage between the conductive substrate and two electrodes located on either side of this substrate. This voltage can be continuous or alternative. Accurate tracking of the currents obtained makes it possible to accurately monitor and control the thicknesses deposited.
- a step of mechanical compaction can be carried out, for example by pressing, before drying in order to improve the quality of the layer; this does not replace the mechanical densification after drying, the effect of which is different.
- PEO functionalised electrolyte or electronic insulator nanoparticles may be deposited, for example by the coating method, dip coating, or by other known deposition techniques of the invention. a person skilled in the art, irrespective of the chemical nature of the nanoparticles used. This deposition process is preferred when electrolyte nanoparticles or electronic insulators functionalized with PEO are little or not electronically charged.
- the dip-coating deposition step of electrolyte nanoparticles or electronic insulators functionalized by PEO followed by the step of drying the layer obtained are repeated as necessary.
- the dip-coating deposition process is a simple, safe, easy to implement and industrialize process, and it makes it possible to obtain a final layer. homogeneous and compact.
- the nanoparticles of electrolyte or electronic insulator functionalized with PEO can be deposited electrophoretically, by the dipping coating process hereinafter “dip-coating”, by the printing process by inkjet hereinafter “ink-jet”, by roll coating (called “roll coating” in English), by curtain coating (called “curtain coating” in English) or by scraping hereinafter “doctor blade” .
- Electrophoretic deposition is a technique that allows uniform deposition over large areas with high deposition rates.
- the coating techniques in particular by dipping, by roller, by curtain or by scraping, make it possible to simplify the management of baths compared to electrophoretic deposition techniques.
- the deposit by inkjet printing makes it possible to make localized deposits.
- Deposits of electrolyte nanoparticles or electronic insulators functionalized with PEO are advantageously carried out by electrophoresis or dip-coating.
- the suspensions of nanoparticles used to make deposits by dip-coating are more concentrated than those used to make deposits by electrophoresis.
- the solid nanoparticle layer obtained After deposition, whether by electrophoresis or dip-coating, the solid nanoparticle layer obtained must be dried. The drying must not induce the formation of cracks. For this reason it is preferred to perform it under conditions of controlled humidity and temperature.
- these layers have electrolytic nanoparticles or crystallized electronic insulators linked together by amorphous PEO.
- these layers have a content of nanoparticles of electrolyte or electronic insulation greater than 35%, preferably greater than 50%, preferably greater than 60% and even more preferably greater than 70% by volume. The use of nanoparticles of electronic insulation limits the self-discharge of the battery and contributes to the amorphization of the PEO.
- the nanoparticles of electrolyte or electronic insulator present in these layers have a size D 5 o less than 100 nm, preferably less than 50 nm and even more preferably less than or equal to 30 nm; this value refers to the "heart” of the nanoparticles "heart - bark”. This particle size ensures good conductivity of the lithium ions between the electrolyte particles and the PEO.
- the electrolyte layer obtained after drying has a thickness of less than 10 ⁇ m, preferably less than 6 ⁇ m, preferably less than 5 ⁇ m, preferably approximately 3 ⁇ m in order to limit the thickness and the weight of the battery without lessen its properties.
- the nanoparticle layer can be densified; this step is optional.
- Densification makes it possible to reduce the porosity of the layer.
- the structure of the layer obtained after densification is continuous, almost without porosity, and the ions can migrate there easily, without the need to add liquid electrolytes containing lithium salts, such liquid electrolytes being at the origin the low thermal resistance of the batteries, and the poor aging behavior of the batteries.
- the layers based on solid electrolyte and PEO obtained after drying and densification generally have a porosity of less than 20%, preferably less than 15% by volume, even more preferably less than 10% by volume, and optimally less than 10% by volume. 5% by volume. This value can be determined by transmission electron microscopy on a section.
- the densification of the layer after its deposition can be carried out by any appropriate means, preferably:
- thermocompression ie by heat treatment under pressure.
- the optimal temperature depends strongly on the chemical composition of the deposited materials, it also depends on the particle sizes and the compactness of the layer.
- a controlled atmosphere is preferably maintained to prevent oxidation and surface pollution of the deposited particles.
- the compaction is performed under a controlled atmosphere and at temperatures between room temperature and the melting temperature of the PEO used; the thermocompression can be carried out at a temperature between room temperature (about 20 ° C) and about 300 ° C; but it is preferred not to exceed 200 ° C (or more preferably 100 C q) in order to avoid degradation of the PEO.
- the densification of electrolyte nanoparticles or electronic insulators functionalized with PEO can be obtained solely by mechanical compression (application of mechanical pressure) because the bark of these nanoparticles comprises PEO, a polymer that is easily deformable at a relatively low pressure.
- the compression is carried out in a pressure range of between 10 MPa and 500 MPa, preferably between 50 MPa and 200 MPa and at a temperature of the order of 20 ° C. to 200 ° C.
- the PEO is amorphous and ensures good ionic contact between the solid electrolyte particles. PEO can thus conduct lithium ions, even in the absence of liquid electrolyte. It promotes the assembly of the lithium ion battery at low temperature, thus limiting the risk of interdiffusion at the interfaces between the electrolytes and the electrodes.
- the electrolyte layer obtained after densification has a thickness less than 10 ⁇ m, preferably less than 6 ⁇ m, preferably less than 5 ⁇ m, preferably about 3 ⁇ m in order to limit the thickness and the weight of the battery without lessen its properties.
- One of the aims of the invention is to provide new electrolytes, preferably in a thin layer, for batteries secondary to lithium ions.
- a suspension of nanoparticles of precursor material of an electrolyte layer according to the invention may be prepared by precipitation or by the solvothermal route, in particular hydrothermally, which leads directly to nanoparticles of good crystallinity.
- the electrolyte layer is deposited by electrophoresis or dip coating on a cathode layer 22 covering a substrate 21 and / or on an anode layer 12 covering a substrate 11; in both cases said substrate must have sufficient conductivity to act as a cathodic or anodic current collector, respectively.
- the assembly of the cell formed by an anode layer 12, the electrolyte layer according to the invention 13, 23 and a cathode layer 22 is made by hot pressing, preferably under an inert atmosphere.
- the temperature is advantageously between 53 and 300, preferably between 20 and 200, and even more preferably between 53 and 100.
- the pressure is advantageously uniaxial and between 10 MPa and 200 MPa, and preferably between 50 MPa and 200 MPa.
- step (5) treatment of the stack of the anode and cathode layers obtained in step (5) by mechanical compression and / or heat treatment so as to assemble the electrolyte layers present on the anode and cathode.
- the anode and cathode layers may be dense electrodes, ie electrodes having a volume porosity of less than 20%, porous electrodes, preferably having an interconnected network of open pores or mesoporous electrodes, preferably having a interconnected network of open mesopores.
- the porous electrodes when used with a liquid electrolyte, parasitic reactions can occur between the electrodes and the electrolyte; these reactions are at least partially irreversible.
- a very thin layer, covering and preferably without defects, of an insulating material is applied.
- this dielectric layer may be a layer of an electrically insulating material deposited on and inside the pores of the porous electrode layer, preferably by the ALD atomic layer deposition technique or by the chemical method in CSD solution. , especially after drying of the porous electrode layer or after consolidation of the porous electrode layer.
- a very thin layer of an electronically insulating material which is preferably an ionic conductor, can be applied to the electrode layer in order to reduce the interfacial resistance existing between the electrodes. dense electrode and the electrolyte.
- This layer of electronically insulating material which is preferably an ionic conductor, advantageously has an electronic conductivity of less than 10 -8 S / cm.
- this deposit is made at least on one face of the electrode, whether it is porous or dense, which forms the interface between the electrode and the electrolyte.
- This layer may, for example, be Al 2 O 3 alumina, SiO 2 silica, or ZrO 2 zirconia.
- this layer of an electronically insulating material may be an ionic conductor, which advantageously has an electronic conductivity of less than 10 8 S / cm.
- This material must be chosen so as not to insert, at the operating voltages of the battery, lithium but only to transport it. It is possible to use, for example, Li 3 P0 4 , Li 3 B0 3 , lithium lanthanum zirconium oxide (called "LLZO"), such as Li 7 La 3 Zr 2 0i 2 , which have a wide range of operating potential.
- LLZO lithium lanthanum zirconium oxide
- lithium lanthanum titanium oxide such as Li 3x La 2/3-x TiO 3
- lithium aluminum titanium phosphate abbreviated “LATP”
- LAGP lithium aluminum germanium phosphate
- this deposit is made by a technique allowing a coating coating (also called “compliant deposit”), i.e. a deposit that faithfully reproduces the atomic topography of the substrate on which it is applied.
- a coating coating also called “compliant deposit”
- the ALD deposition technique is layer by layer, by a cyclic process, and allows a coating coating that faithfully reproduces the topography of the substrate; it covers the entire surface of the electrodes.
- This coating coating typically has a thickness between 1 nm and 5 nm.
- the CSD deposition technique makes it possible to produce a coating which faithfully reproduces the topography of the substrate; it covers the entire surface of the electrodes.
- This coating coating typically has a thickness less than 5 nm, preferably between 1 nm and 5 nm.
- the primary diameter D 5 o of the particles of electrode material used to produce them is at least 10 nm in order to prevent the layer of the electronically insulating material, preferably ionic conductor, from blocking the open porosity of the electrode layer.
- the layer of an electronically insulating material preferably an ionic conductor, must only be deposited on electrodes that do not contain an organic binder. Indeed the deposition by ALD is carried out at a temperature typically between 100 ° C and 300 53. At this temperature the organic materials forming the binder (for example the polymers contained in the electrodes made by ink casting tape) are likely to break down and will pollute the ALD reactor. On the other hand, the presence of residual polymers in contact with the electrode active material particles can prevent the ALD coating from coating all of the particle surfaces, which affects its effectiveness. By way of example, an alumina layer with a thickness of the order of 1.6 nm may be suitable.
- the electrode is a cathode it can be made from a cathode material P chosen from:
- LiMn 2 0 4 the oxide LiMn 2 0 4, ⁇ i Mh + c 2 - c q4 with O ⁇ x ⁇ 0.15, LiCo0 2, LiNi0 2, L ⁇ mni, 5 Ni 0, 5O 4 UMni, 5 Ni 0, 5 x X x O4
- the electrode is an anode it can be made from anode material P chosen from:
- lithium iron phosphate (of typical formula LiFePO 4 );
- mixed oxynitrides of silicon and tin (of standard formula Si a Sn b Y y N z with a> 0, b> 0, a + b ⁇ 2, 0 ⁇ y ⁇ 4, 0 ⁇ z ⁇ 3) (also called SiTON), and in particular SiSn 0, 87O1, 2 Ni, 72; and oxynitrides, carbides typical formula Si a Sn b C c O y N z with a> 0, b> 0, a + b ⁇ 2, 0 ⁇ c ⁇ 10, 0 ⁇ y ⁇ 24, 0 ⁇ z ⁇ 17;
- the composite oxides TiNb 2 0 7 comprising between 0% and 10% by mass of carbon, preferably the carbon being selected from graphene and carbon nanotubes.
- an electrolyte according to the invention can be produced on dense, porous, preferably mesoporous electrodes, coated or not with a layer of an electronically insulating material, preferably an ionic conductor by ALD or by CSD.
- this battery advantageously contains an anode layer 12 and a porous cathode layer 22, preferably mesoporous, and an electrolyte according to the invention.
- the anode and cathode layers, coated or not with a layer by ALD or by CSD of an electronically insulating material, preferably an ionic conductor, then covered with an electrolyte layer according to the invention are pressed. hot to promote assembly of the cell.
- a rigid multilayer system consisting of one or more assembled cells is obtained.
- ALD electronically insulating material
- CSD electronically insulating material
- this treatment makes it possible to cover only the accessible surfaces of the mesoporous structure, ie the surfaces which will subsequently be in contact with phases carrying lithium ions.
- This deposit improves the performance of lithium ion batteries comprising at least one porous electrode.
- the improvement observed consists essentially in a reduction of faradic reactions at the interface between the lithium ion carrier phases and the electrode.
- this deposit is made by a technique allowing a coating coating (also called “compliant deposit”), ie a deposit that faithfully reproduces the atomic topography of the substrate on which it is applied.
- a coating coating also called “compliant deposit”
- ALD and CSD deposition techniques make it possible to produce a coating which covers the entire surface of the porous electrodes.
- This coating coating typically has a thickness less than 5 nm, preferably between 1 nm and 5 nm.
- the production of a battery comprising dense electrodes and an electrolyte according to the invention will be preferred.
- a battery comprising at least one porous electrode, preferably mesoporous and an electrolyte according to the invention has increased performance, including a high power density.
- a lithium ion battery according to the invention comprising at least one porous electrode, preferably mesoporous. This process comprises the steps of:
- step (8) drying the layer thus obtained in step (7), preferably under a stream of air,
- step (9) to assemble the films obtained in step (8) present on the anode and cathode layers,
- step (10) Impregnation of the structure obtained in step (10) or after step (1 1) by a phase carrying lithium ions leading to obtaining an impregnated structure, preferably a cell.
- step (11) Impregnation of the structure obtained in step (10) or after step (1 1) by a phase carrying lithium ions leading to obtaining an impregnated structure, preferably a cell.
- step (11) Impregnation of the structure obtained in step (10) or after step (1 1) by a phase carrying lithium ions leading to obtaining an impregnated structure, preferably a cell.
- a constituent stack of a battery by hot pressing can be encapsulated in an encapsulation system as presented hereinafter, then cut according to cutting planes. allowing to obtain unitary battery components, with the bare on each of the cutting planes of the anode and cathode connections 50 of the battery as indicated hereinafter, then impregnated with a phase carrying lithium ions before the deposition of the termination system, as indicated below.
- This phase may be a solution formed by a lithium salt dissolved in an organic solvent or a mixture of organic solvents, and / or dissolved in a polymer containing at least one lithium salt, and / or dissolved in an ionic liquid (ie a molten lithium salt) containing at least one lithium salt.
- This phase can also be a solution formed from a mixture of these components.
- the carrier phase of lithium ions makes it possible to impregnate the porous electrodes when such electrodes are used.
- the electrolyte layer according to the invention is not impregnated by the carrier phase of lithium ions.
- the carrier phase of lithium ions may be an ionic liquid containing lithium salts, possibly diluted with an organic solvent or with a mixture of organic solvents containing a lithium salt which may be different from that dissolved in the ionic liquid.
- the ionic liquid consists of a cation associated with an anion; this anion and this cation are chosen so that the ionic liquid is in the liquid state in the operating temperature range of the accumulator.
- the ionic liquid has the advantage of having high thermal stability, reduced flammability, nonvolatility, low toxicity and good wettability of ceramics, which are materials that can be used as electrode materials.
- the mass percentage of ionic liquid contained in the lithium ion carrier phase may be greater than 50%, preferably greater than 60% and even more preferably greater than 70%, and this in contrast to lithium ion batteries.
- lithium of the prior art where the mass percentage of ionic liquid in the electrolyte must be less than 50% by mass so that the battery retains a high capacity and a high voltage discharge and a good stability in cycling. Above 50% by mass the capacity of the battery of the prior art is degraded, as indicated in the application US 2010/209 783 A1. This can be explained by the presence of polymeric binders within the electrolyte of the battery of the prior art; these binders are weakly wetted by the ionic liquid inducing poor ionic conduction within the carrier phase of lithium ions thus causing degradation of the capacity of the battery.
- Batteries using a porous electrode are preferably free of binder.
- these batteries can employ a phase carrying lithium ions comprising more than 50% by mass of at least one ionic liquid without degrading the final capacity of the battery.
- the carrier phase of lithium ions may comprise a mixture of several ionic liquids.
- the ionic liquid may be a type 1-ethyl-3-methylimidazolium cation (also called EMI +) and / or n-propyl-n-methylpyrrolidinium (also called PYRi3 + ) and / or n-butyl-n- methylpyrrolidinium (also called PYR I4 + ), associated with bis (trifluoromethanesulfonyl) imide (TFSL) and / or bis (fluorosulfonyl) imide (FSI) anions.
- EMI + type 1-ethyl-3-methylimidazolium cation
- PYRi3 + n-propyl-n-methylpyrrolidinium
- PYR I4 + n-butyl-n- methylpyrrolidinium
- a lithium salt such as LiTFSI may be dissolved in the ionic liquid which serves as a solvent or in a solvent such as ⁇ -butyrolactone.
- ⁇ -Butyrolactone prevents the crystallization of ionic liquids inducing a greater temperature operating range of the latter, especially at low temperatures.
- the carrier phase of lithium ions may be an electrolytic solution comprising PYR14TFSI and LiTFSI; these abbreviations will be defined below.
- the lithium ion carrier phase comprises a solid electrolyte such as LiBH 4 or a mixture of LiBH 4 with one or more compounds chosen from LiCl, LiR and LiBr.
- LiBH 4 is a good conductor of lithium and has a low melting point facilitating its impregnation in porous electrodes, especially by soaking. Due to its extremely reducing properties, LiBH 4 is not widely used as an electrolyte.
- the use of a protective film on the surface of the porous lithiated phosphate electrodes prevents the reduction of the electrode materials, in particular cathode materials, by the LiBH 4 and avoids the degradation of the electrodes.
- the carrier phase of lithium ions comprises at least one ionic liquid, preferably at least one ionic liquid at ambient temperature, such as PYR14TFSI, optionally diluted in at least one solvent, such as ⁇ -butyrolactone.
- the carrier phase of lithium ions comprises between 10% and 40% by weight of a solvent, preferably between 30 and 40% by weight of a solvent, and even more preferably between 30 and 40% by weight of y-butyrolactone. .
- the carrier phase of lithium ions comprises more than 50% by weight of at least one ionic liquid and less than 50% of solvent, which limits the risks of safety and ignition in the event of malfunction of the batteries comprising such carrier phase of lithium ions.
- the carrier phase of lithium ions comprises:
- a solvent preferably between 30 and 40% by weight of y-butyrolactone, and more than 50% by weight of at least one ionic liquid, preferably more than 50% by weight of PYR14TFSI.
- the carrier phase of lithium ions may be an electrolytic solution comprising PYR14TFSI, LiTFSI and g-butyrolactone, preferably an electrolytic solution comprising approximately 90% by weight of PYR14TFSI, 0.7 M of LiTFSI and 10% by mass of y-butyrolactone.
- the porous electrodes are capable of absorbing a liquid phase by simple capillarity when the average diameter D 5 o of the pores is between 2 nm and 80 nm, preferably between 2 nm and 50 nm, preferably between 6 nm and 30 nm, preferably between 8 nm and 20 nm. This effect is quite unexpected and is particularly favored with the decrease of the pore diameter of these electrodes.
- the pores of this assembly can easily be wetted by an ionic liquid, by mixtures of ionic liquids or by a solution comprising at least 50% by weight of at least one diluted ionic liquid. with an organic solvent or diluted with a mixture of organic solvents.
- the pores of the porous electrode preferably mesoporous, are impregnated with an electrolyte, preferably a phase carrying lithium ions such as an ionic liquid containing lithium salts, possibly diluted with an organic solvent or a mixture of organic solvents containing a lithium salt which may be different from that dissolved in the ionic liquid.
- a lithium ion battery cell of very high power density is thus obtained.
- the battery or assembly a rigid multilayer system consisting of one or more assembled cells, coated or not with a dielectric layer, optionally impregnated with a phase carrying lithium ions, must then be encapsulated by a method suitable for ensure its protection from the atmosphere.
- the encapsulation system comprises at least one layer, and preferably represents a stack of several layers. If the encapsulation system consists of a single layer, it must be deposited by ALD or be in parylene and / or polyimide. These encapsulation layers must be chemically stable, withstand high temperatures and be impermeable to the atmosphere (barrier layers).
- said at least one encapsulation layer covers four of the six faces of said battery, the other two faces of the battery being coated by the terminations.
- the battery or the assembly may be covered with an encapsulation system formed by a stack of several layers, namely a sequence, preferably z sequences, comprising:
- a first covering layer preferably chosen from parylene, type F parylene, polyimide, epoxy resins, silicone, polyamide and / or a mixture thereof, deposited on the stack of sheets of anode and cathode,
- a second covering layer composed of an electrically insulating material deposited by depositing atomic layers on said first covering layer.
- This sequence can be repeated z times with z> 1.
- This multilayer sequence has a barrier effect. The more the sequence of the encapsulation system will be repeated, the more this barrier effect will be important. It will be all the more important that the thin films deposited will be numerous.
- the first covering layer is a polymeric layer, for example silicone (deposited for example by impregnation or plasma-enhanced chemical vapor deposition from hexamethyldisiloxane (HMDSO)), or epoxy resin, or polyimide , polyamide, or poly-para-xylylene (better known as parylene), preferably based on parylene and / or polyimide.
- This first covering layer makes it possible to protect the sensitive elements of the battery of its environment.
- the thickness of said first cover layer is preferably between 0.5 ⁇ m and 3 ⁇ m.
- the first covering layer may be parylene type C, parylene type D, parylene type N (CAS 1633-22-3), type F parylene or a mixture of parylene type C, D , N and / or F.
- Parylene also known as polyparaxylylene or poly (p-xylylene)
- Parylene is a dielectric, transparent, semi-crystalline material which exhibits high thermodynamic stability, excellent solvent resistance and very low permeability. Parylene also has barrier properties to protect the battery from its external environment. The protection of the battery is increased when this first covering layer is made from type F parylene. It can be deposited under vacuum, by a chemical vapor deposition (CVD) technique.
- CVD chemical vapor deposition
- This first encapsulation layer is advantageously obtained from the condensation of gaseous monomers deposited by chemical vapor deposition (CVD) on the surfaces, which allows to have a conformal, thin and uniform recovery of all accessible surfaces of the object. It makes it possible to follow the variations of volume of the battery during its operation and facilitates the clean cutting of the batteries due to its elastic properties.
- the thickness of this first encapsulation layer is between 2 ⁇ m and 10 ⁇ m, preferably between 2 ⁇ m and 5 ⁇ m and even more preferably around 3 ⁇ m. It makes it possible to cover all the accessible surfaces of the stack, to close only on the surface access to the pores of these accessible surfaces and to standardize the chemical nature of the substrate. The first cover layer does not enter the pores of the battery or the assembly, the size of the deposited polymers being too large for them to enter the pores of the stack.
- This first covering layer is advantageously rigid; it can not be considered a soft surface.
- the encapsulation can thus be carried out directly on the stacks, the coating being able to penetrate all the available cavities.
- a first layer of parylene such as a layer of parylene C, of parylene D, a layer of parylene N (CAS number: 1633-22-3) or a layer comprising a mixture of parylene, is deposited.
- Parylene also known as polyparaxylylene or poly (p-xylylene)
- Parylene is a dielectric, transparent, semi-crystalline material with high thermodynamic stability, excellent solvent resistance and very low permeability. .
- This parylene layer protects the sensitive elements of the battery from their environment. This protection is increased when this first encapsulation layer is made from N. parylene.
- a first polyimide layer is deposited. This layer of polyimide protects the sensitive elements of the battery of their environment.
- the first encapsulation layer consists of a first layer of polyimide, preferably about 1 ⁇ m thick on which is deposited a second layer of parylene, preferably about 2 pm thick.
- This protection is increased when this second layer of parylene, preferably about 2 .mu.m thick is made from parylene N.
- the polyimide layer associated with the parylene layer improves the protection of the sensitive elements of the battery of their environment.
- this first layer when it is based on parylene, does not have sufficient stability in the presence of oxygen.
- this first layer is based on polyimide, it does not have a sufficient seal, especially in the presence of water. For these reasons, a second layer is deposited which coats the first layer.
- a second covering layer composed of an electrically insulating material may be deposited by a conformal deposition technique, such as the deposition of atomic layers (ALD) on the first layer.
- ALD atomic layers
- the growth of the layer deposited by ALD is influenced by the nature of the substrate.
- a layer deposited by ALD on a substrate having different zones of different chemical natures will have an inhomogeneous growth, which can cause a loss of integrity of this second protective layer.
- This second layer deposited on the first layer of parylene and / or polyimide protects the first layer of parylene and / or polyimide against the air and improves the life of the encapsulated battery.
- ALD deposition techniques are particularly well suited to cover surfaces with a high roughness in a completely sealed and compliant manner. They make it possible to produce conformal layers, free of defects, such as holes (so-called "pinhole free” layers, and represent very good barriers. Their WVTR coefficient is extremely low. The WVTR coefficient (water vapor transmission rate) is used to evaluate the water vapor permeance of the encapsulation system. The lower the WVTR coefficient, the more the encapsulation system is watertight. By way of example, an Al 2 O 3 layer of 100 nm thick deposited by ALD exhibits a water vapor permeation of 0.00034 g / m 2 d.
- the second covering layer may be ceramic material, vitreous material or glass-ceramic material, for example in the form of oxide, Al 2 0 3 type , nitride, phosphates, oxynitride, or siloxane.
- This second encapsulation layer has a thickness of less than 200 nm, preferably between 5 nm and 200 nm, more preferably between 10 nm and 100 nm, between 10 nm and 50 nm, and still more preferably of the order of fifty nanometers.
- This second covering layer deposited by ALD makes it possible, on the one hand, to seal the structure, ie to prevent the migration of water inside the structure and, on the other hand, to protect the first one.
- covering layer preferably parylene and / or polyimide, preferably type F parylene, of the atmosphere in order to prevent its degradation.
- a third covering layer is deposited on the second covering layer or on an encapsulation system formed by a stack of several layers as described above, namely a sequence, preferably z sequences. encapsulation system with z> 1, to increase the protection of the battery cells of their external environment.
- this third layer is made of polymer, for example silicone (deposited for example by impregnation or plasma-enhanced chemical vapor deposition from hexamethyldisiloxane (HMDSO, CAS No. 107-46-0)), or epoxy resin, or parylene, or polyimide.
- the encapsulation system 30 may comprise an alternating succession of layers of parylene and / or polyimide, preferably about 3 ⁇ m thick, and layers composed of an electrically insulating material such as inorganic layers. consistently deposited by ALD as previously described to create a multi-layer encapsulation system.
- the encapsulation system may advantageously comprise a first layer of parylene and / or polyimide, preferably about 3 ⁇ m thick, a second layer composed of an electrically isolator, preferably an inorganic layer, ALD-conformally deposited on the first layer, a third layer of parylene and / or polyimide, preferably about 3 ⁇ m thick deposited on the second layer and a fourth layer composed of of an electrically insulating material conformably deposited by ALD on the third layer.
- the battery or the assembly encapsulated in this sequence of the encapsulation system 30, preferably in z sequences, can then be coated with a final covering layer so as to mechanically protect the thus encapsulated stack and possibly give an aesthetic appearance.
- This last layer of cover protects and improves the life of the battery.
- this last covering layer is also chosen to withstand a high temperature, and has sufficient mechanical strength to protect the battery during its subsequent use.
- the thickness of this last covering layer is between 1 ⁇ m and 50 ⁇ m. Ideally, the thickness of this last cover layer is about 10-15 pm, such a range of thickness can protect the battery against mechanical damage.
- this last covering layer is deposited on an encapsulation system 30 formed by a stack of several layers as previously described, namely a sequence, preferably z sequences of the encapsulation system with z> 1, of preferably on this alternating succession of layers of parylene and / or polyimide, preferably about 3 ⁇ m thick and inorganic layers deposited conformally by ALD, to increase the protection of the battery cells of their external environment and protect them against mechanical damage.
- This last encapsulation layer preferably has a thickness of about 10-15 ⁇ m.
- This last covering layer is preferably based on epoxy resin, polyethylene naphthalate (PEN), polyimide, polyamide, polyurethane, silicone, sol-gel silica or organic silica.
- this last covering layer is deposited by dipping.
- this last layer is made of polymer, for example silicone (deposited for example by dipping or plasma-enhanced chemical vapor deposition from hexamethyldisiloxane (HMDSO)), or epoxy resin, or parylene, or polyimide.
- a silicone layer typically thickness about 15 ⁇ m
- the encapsulation system 30 shown in FIG. 1 advantageously comprises a stack of several layers, namely a sequence, preferably z sequences with z> 1, comprising:
- a first covering layer preferably chosen from parylene, type F parylene, polyimide, epoxy resins, silicone, polyamide and / or a mixture thereof, deposited on the stack of sheets of anode and cathode,
- a second covering layer composed of an electrically insulating material deposited by depositing atomic layers on said first covering layer
- encapsulation of the battery is performed on four of the six faces of the stack.
- the encapsulation layers surround the periphery of the stack, the rest of the protection against the atmosphere being provided by the layers obtained by the terminations.
- the thus encapsulated stack is then cut according to section planes making it possible to obtain unitary battery components, with the exposure on each of the section planes of the anode and cathode connections 50 of the battery, so that the encapsulation system 30 covers four of the six faces of said battery, preferably in a continuous manner, so that the system can be assembled seamlessly, the other two sides of the battery being subsequently coated by the terminations 40 .
- the stack thus encapsulated and cut when it comprises porous electrodes can be impregnated, under anhydrous atmosphere, with a phase carrying lithium ions such as an ionic liquid containing lithium salts. , possibly diluted in an organic solvent or a mixture of organic solvents containing a lithium salt which may be different from that dissolved in the ionic liquid, as indicated in the present application.
- the impregnation may be carried out by dipping in an electrolytic solution such as an ionic liquid containing lithium salts, possibly diluted in an organic solvent or a mixture of organic solvents containing a lithium salt that may be different from that dissolved in the liquid. ionic.
- the ionic liquid returns instantly by capillarity in the porosities.
- terminations 40 are added to establish the electrical contacts necessary for the proper functioning of the battery.
- the battery comprises terminations 40 at the level where the cathodic current collectors, respectively anodic, are apparent.
- the anode connections and the cathode connections are on the opposite sides of the stack.
- On and around these connections 50 is deposited a termination system 40.
- the connections can be metallized using deposition techniques. plasma known to those skilled in the art, preferably by ALD and / or by immersion in a conductive epoxy resin (loaded with silver) and / or a molten tin bath.
- the terminations consist of a stack of layers successively comprising a first thin layer of electronically conductive coating, preferably metallic, deposited by ALD, a second layer of silver-filled epoxy resin deposited on the first layer and a third layer.
- the first conductive layer deposited by ALD serves to protect the battery section from moisture.
- This first conductive layer deposited by ALD is optional. It increases the battery life of the battery by reducing the WVTR at the termination.
- This first thin covering layer may in particular be metallic or based on metal nitride.
- the second layer of epoxy resin loaded with silver makes it possible to provide "flexibility" to the connectors without breaking the electrical contact when the electrical circuit is subjected to thermal and / or vibratory stresses.
- the third layer of tin metallization serves to ensure the solderability of the battery.
- this third layer may be composed of two layers of different materials.
- This layer is made of nickel and is made by electrolytic deposition.
- the nickel layer serves as a thermal barrier and protects the remainder of the diffusion component during the reflow assembly steps.
- the last layer, deposited on the nickel layer is also a metallization layer, preferably tin to make the compatible interface assemblies by reflow.
- This layer of tin can be deposited either by dipping in a bath of molten tin or by electrodeposition; these techniques are known as such.
- Such a layer can be made by electrodeposition instead of tin.
- the terminations 40 may consist of a stack of layers successively comprising a layer of silver-filled epoxy resin and a second layer based on tin or nickel deposited on the first layer.
- the terminations 40 may consist of a stack of layers successively comprising a silver-filled epoxy resin layer, a second nickel-based layer deposited on the first layer and a third layer based on tin or copper.
- the terminations 40 may consist of different layers which are, respectively, in a nonlimiting manner, a layer of conductive polymer such as a silver-filled epoxy resin, a nickel layer and a protective layer. 'tin.
- the terminations 40 consist, in the vicinity of the cathode and anode connections, of a first stack of layers successively comprising a first layer of a graphite-loaded material, preferably a graphite filled epoxy resin. and a second layer comprising metallic copper obtained from an ink charged with copper nanoparticles deposited on the first layer.
- This first stack of terminations is then sintered by infra-red flash lamp so as to obtain a covering of the cathodic and anodic connections by a layer of metallic copper.
- the terminations may additionally comprise a second stack of layers disposed on the first stack of terminations successively comprising a first layer of deposited tin-zinc alloy, preferably by dipping. in a bath of molten tin-zinc, in order to ensure the sealing of the battery at a lower cost and a second layer based on pure tin deposited by electroplating or a second layer comprising a silver-based alloy, of palladium and copper deposited on this first layer of the second stack.
- the terminations 40 make it possible to resume the alternately positive and negative electrical connections on each end of the battery. These terminations make it possible to make the electrical connections in parallel between the different battery elements. For this, only the cathodic connections go out on one end, and the anode connections are available on another end.
- the anode and cathode connections are on the opposite sides of the stack.
- Example 1 Manufacture of a Lithium Phosphate / PEO Electrolyte Layer
- solution B 4.0584 g of H 3 PO 4 were diluted in 105.6 ml of water, then 45.6 ml of ethanol was added to this solution in order to obtain a second solution, hereinafter referred to as solution B.
- Solution B was then added, with vigorous stirring, to solution A.
- the reaction medium was homogenized for 5 minutes and then kept for 10 minutes with magnetic stirring. It was allowed to settle for 1 to 2 hours. The supernatant was discarded and the remaining suspension was centrifuged for 10 minutes at 6000 rpm. Then 300 ml of water were added to return the precipitate in suspension (use of a sonotrode, magnetic stirring).
- the colloidal suspension thus obtained comprises nanoparticles of Li 3 PO 4 at a concentration of 10 g / l.
- electrolyte nanoparticles previously obtained in suspension at a concentration of 10 g / l were then functionalized with methoxy-PE05000-phosphonate An aqueous solution of this molecule was added to a colloidal suspension of electrolyte nanoparticles.
- reaction medium was stirred for 1 hour at 70 ° so that the phosphonate groups are grafted on the surface of the Li 3 PO electrolyte nanoparticles.
- the nanoparticles thus functionalized were then purified by successive cycles of centrifugation and redispersion so as to separate the functionalized particles from the unreacted molecules present in the supernatant. After centrifugation, the supernatant was removed. The pellet comprising the functionalized particles was redispersed in an amount of solvent to reach the desired solids content.
- a suspension of the anode material was prepared by grinding / dispersing a powder of Li 4 Ti 5 O 12 in absolute ethanol at about 10 g / L with a few ppm of citric acid. Milling was carried out so as to obtain a stable suspension with a particle size of 5 D o less than 70 nm.
- anode layer 12 has been deposited an anode layer 12 by electrophoresis nanoparticles of Li 4 Ti 5 0i 2 contained in the suspension; this layer was deposited on both sides of a first conductive substrate with a thickness of 1 ⁇ m; it was dried and then heat treated to about 60053.
- This anode layer 12 was a so-called "dense" layer, having undergone a thermal consolidation step which leads to the increase of the density of the layer.
- the anode was then coated with a protective coating of Li 3 PO at a thickness of 10 nm deposited by ALD.
- a slurry at about 10 g / L of cathode material was prepared by grinding / dispersing a LiMn 2 powder in water. Grinding the slurry was formed to obtain a stable suspension with a particle size of 5 D o less than 50 nm.
- a cathode was prepared by electrophoretic deposition of LiMn 2 0 4 nanoparticles contained in the suspension described above, in the form of a thin film deposited on both sides of a second conductive substrate; this 1 ⁇ m thick cathode layer was then heat treated at about 600 ° C.
- This layer cathode was a so-called "dense" layer, having undergone a thermal consolidation step that leads to the increase of the density of the layer.
- the cathode was then coated with a protective coating of ⁇ 3 R0 4 with a thickness of 10 nm deposited by ALD.
- the nanoparticles thus functionalised in suspension at 10 g / l in ethanol were deposited by electrophoresis on the first (respectively second) conductive substrate previously covered with an anode layer 12 as indicated previously in point 2 of the example below. above, respectively of cathode as indicated previously in point 3 of the example above, by applying between the substrate and a counter-electrode, both immersed in the colloidal suspension, a voltage of 45 V until a layer of 1.4 ⁇ m thick.
- Example 1 .2 and the cathode obtained in Example 1.3 were stacked on their electrolyte faces and the assembly was kept under pressure at 50 MPa for 15 minutes at 20053; a lithium ion battery was thus obtained which could be charged and discharged in many cycles.
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- Microelectronics & Electronic Packaging (AREA)
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- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1853923A FR3080952B1 (fr) | 2018-05-07 | 2018-05-07 | Electrolyte pour dispositifs electrochimiques en couches minces |
PCT/FR2019/051032 WO2019215410A1 (fr) | 2018-05-07 | 2019-05-06 | Electrolyte solide pour dispositifs electrochimiques |
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EP3766119A1 true EP3766119A1 (fr) | 2021-01-20 |
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EP19728502.6A Pending EP3766119A1 (fr) | 2018-05-07 | 2019-05-06 | Electrolyte solide pour dispositifs electrochimiques |
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US (1) | US20210104777A1 (fr) |
EP (1) | EP3766119A1 (fr) |
JP (1) | JP2021522661A (fr) |
CN (1) | CN112042031A (fr) |
CA (1) | CA3098637A1 (fr) |
FR (1) | FR3080952B1 (fr) |
SG (1) | SG11202010867QA (fr) |
WO (1) | WO2019215410A1 (fr) |
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US11594718B2 (en) * | 2019-05-23 | 2023-02-28 | Sila Nanotechnologies, Inc. | Densified battery electrodes with electrode parts having different porosities and methods thereof |
IL293348A (en) | 2019-12-24 | 2022-07-01 | I Ten | A battery with a reinforced wrapping system in the contact connectors |
CA3162319A1 (fr) | 2019-12-24 | 2021-07-01 | I-Ten | Batterie, notamment en couches minces, avec un nouveau systeme d'encapsulation |
FR3105605A1 (fr) * | 2019-12-24 | 2021-06-25 | I-Ten | Batterie, notamment en couches minces, avec un nouveau système d’encapsulation |
FR3105602B1 (fr) * | 2019-12-24 | 2024-05-10 | I Ten | Dispositif électrochimique de type batterie, comprenant des moyens d’étanchéité perfectionnés, et son procédé de fabrication |
FR3105604B1 (fr) * | 2019-12-24 | 2023-06-09 | I Ten | Batterie avec un systeme d’encapsulation renforcee au niveau des organes de contact |
FR3110774B1 (fr) * | 2020-05-20 | 2022-04-15 | I Ten | Procédé de fabrication d’une batterie à ions de lithium |
FR3109670B1 (fr) | 2020-04-28 | 2022-10-14 | I Ten | Procédé de fabrication d’un ensemble électrode poreuse et séparateur, un ensemble électrode poreuse et séparateur, et microbatterie contenant un tel ensemble |
FR3109671B1 (fr) | 2020-04-28 | 2022-10-14 | Hfg | Procédé de fabrication d’un ensemble électrode poreuse et séparateur, un ensemble électrode poreuse et séparateur, et dispositif electrochimique contenant un tel ensemble |
FR3111741B1 (fr) * | 2020-06-23 | 2022-12-30 | Hfg | Anode de forte densite d’energie et de puissance pour batteries |
FR3111740B1 (fr) * | 2020-06-23 | 2022-12-30 | I Ten | Anode de forte densite d’energie et de puissance pour batteries |
CN113328136A (zh) * | 2021-05-28 | 2021-08-31 | 王伟东 | 一种固态电解质llzo粉末及其制备方法 |
WO2023091251A2 (fr) * | 2021-10-15 | 2023-05-25 | The Texas A&M University System | Supercondensateurs à ions zinc structuraux (zihsc) |
CN114203967B (zh) * | 2021-11-05 | 2024-03-15 | 东方电气集团科学技术研究院有限公司 | 一种胶体电泳的新型锂离子电池负极极片制备方法 |
ES2944407B2 (es) * | 2021-12-20 | 2023-12-28 | M Torres Disenos Ind S A Unipersonal | Electrolito solido, su metodo de fabricacion, y su metodo de impregnacion |
CN115172759B (zh) * | 2022-09-06 | 2022-12-20 | 深圳海润新能源科技有限公司 | 集流体、电池、集流体制备方法及电池制备方法 |
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JP3643289B2 (ja) | 1999-04-30 | 2005-04-27 | 株式会社オハラ | ガラスセラミックス複合電解質、及びリチウム二次電池 |
JP4501247B2 (ja) * | 2000-07-27 | 2010-07-14 | 株式会社デンソー | 電池用電極の製造方法および電池用電極の製造装置 |
JP4686825B2 (ja) | 2000-07-31 | 2011-05-25 | 株式会社デンソー | 固体電解質層付き電池用電極の製造方法 |
JP4777593B2 (ja) | 2002-11-29 | 2011-09-21 | 株式会社オハラ | リチウムイオン二次電池の製造方法 |
WO2004058639A1 (fr) * | 2002-12-25 | 2004-07-15 | E-Tec Co., Ltd. | Particule fine d'oxyde metallique, microcapsule d'oxyde metallique, particule fine d'hydroxyde metallique, et procedes de production associes |
FR2917537B1 (fr) | 2007-06-15 | 2009-09-25 | Saft Groupe Sa | Accumulateur lithium-ion contenant un electrolyte comprenant un liquide ionique |
FR2925227B1 (fr) * | 2007-12-12 | 2009-11-27 | Commissariat Energie Atomique | Dispositif electrochimique au lithium encaspule. |
US9142863B2 (en) * | 2009-01-15 | 2015-09-22 | Cornell University | Nanoparticle organic hybrid materials (NOHMs) and compositions and uses of NOHMs |
CN102237320A (zh) * | 2010-04-30 | 2011-11-09 | 财团法人工业技术研究院 | 电子元件封装结构及其制造方法 |
FR2982083B1 (fr) * | 2011-11-02 | 2014-06-27 | Fabien Gaben | Procede de realisation de films minces d'electrolyte solide pour les batteries a ions de lithium |
FR2981952B1 (fr) * | 2011-11-02 | 2015-01-02 | Fabien Gaben | Procede de realisation de couches minces denses par electrophorese |
TW201322382A (zh) * | 2011-11-17 | 2013-06-01 | Wintek Corp | 電致發光顯示裝置 |
FR3002695B1 (fr) | 2013-02-28 | 2021-04-02 | I Ten | Procede de fabrication d'une batterie monolithique entierement solide |
FR3011391B1 (fr) * | 2013-09-27 | 2015-09-18 | Commissariat Energie Atomique | Procede de realisation d'une electrode pour batterie lithium-ion |
FR3023418B1 (fr) | 2014-07-01 | 2016-07-15 | I Ten | Batterie entierement solide comprenant un electrolyte en materiau polymere solide reticule |
FR3023417B1 (fr) | 2014-07-01 | 2016-07-15 | I-Ten | Batterie entierement solide comprenant un electrolyte solide et une couche de materiau polymere solide |
FR3046498B1 (fr) | 2015-12-31 | 2019-11-29 | I-Ten | Batterie entierement solide comprenant un electrolyte solide et une couche de materiau conducteur ionique |
-
2018
- 2018-05-07 FR FR1853923A patent/FR3080952B1/fr active Active
-
2019
- 2019-05-06 CN CN201980029320.0A patent/CN112042031A/zh active Pending
- 2019-05-06 WO PCT/FR2019/051032 patent/WO2019215410A1/fr unknown
- 2019-05-06 US US17/049,983 patent/US20210104777A1/en active Pending
- 2019-05-06 CA CA3098637A patent/CA3098637A1/fr active Pending
- 2019-05-06 SG SG11202010867QA patent/SG11202010867QA/en unknown
- 2019-05-06 JP JP2020560766A patent/JP2021522661A/ja active Pending
- 2019-05-06 EP EP19728502.6A patent/EP3766119A1/fr active Pending
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JP2021522661A (ja) | 2021-08-30 |
WO2019215410A1 (fr) | 2019-11-14 |
US20210104777A1 (en) | 2021-04-08 |
CN112042031A (zh) | 2020-12-04 |
FR3080952B1 (fr) | 2020-07-17 |
FR3080952A1 (fr) | 2019-11-08 |
SG11202010867QA (en) | 2020-12-30 |
CA3098637A1 (fr) | 2019-11-14 |
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