EP3956935A1 - Lithium-ionen-batterien - Google Patents
Lithium-ionen-batterienInfo
- Publication number
- EP3956935A1 EP3956935A1 EP19721552.8A EP19721552A EP3956935A1 EP 3956935 A1 EP3956935 A1 EP 3956935A1 EP 19721552 A EP19721552 A EP 19721552A EP 3956935 A1 EP3956935 A1 EP 3956935A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- anode
- organic
- ion batteries
- separator
- 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 63
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 59
- 239000003792 electrolyte Substances 0.000 claims abstract description 46
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 150000002823 nitrates Chemical class 0.000 claims abstract description 25
- 150000002826 nitrites Chemical class 0.000 claims abstract description 24
- 229910001959 inorganic nitrate Inorganic materials 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 30
- 239000010405 anode material Substances 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 9
- 150000001447 alkali salts Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- LNNXFUZKZLXPOF-UHFFFAOYSA-N 2-methylpropyl nitrate Chemical compound CC(C)CO[N+]([O-])=O LNNXFUZKZLXPOF-UHFFFAOYSA-N 0.000 claims description 2
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 claims description 2
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 2
- IYYGLLJDALWAMD-UHFFFAOYSA-N benzyl nitrite Chemical compound O=NOCC1=CC=CC=C1 IYYGLLJDALWAMD-UHFFFAOYSA-N 0.000 claims description 2
- QQHZPQUHCAKSOL-UHFFFAOYSA-N butyl nitrate Chemical compound CCCCO[N+]([O-])=O QQHZPQUHCAKSOL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- APNSGVMLAYLYCT-UHFFFAOYSA-N isobutyl nitrite Chemical compound CC(C)CON=O APNSGVMLAYLYCT-UHFFFAOYSA-N 0.000 claims description 2
- GAPFWGOSHOCNBM-UHFFFAOYSA-N isopropyl nitrate Chemical compound CC(C)O[N+]([O-])=O GAPFWGOSHOCNBM-UHFFFAOYSA-N 0.000 claims description 2
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 claims description 2
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 2
- 229940082615 organic nitrates used in cardiac disease Drugs 0.000 claims description 2
- HTIXSIBTBYVJHX-UHFFFAOYSA-N phenyl nitrite Chemical compound O=NOC1=CC=CC=C1 HTIXSIBTBYVJHX-UHFFFAOYSA-N 0.000 claims description 2
- JNTOKFNBDFMTIV-UHFFFAOYSA-N propyl nitrate Chemical compound CCCO[N+]([O-])=O JNTOKFNBDFMTIV-UHFFFAOYSA-N 0.000 claims description 2
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 claims description 2
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 28
- 229910052744 lithium Inorganic materials 0.000 description 23
- 229910013553 LiNO Inorganic materials 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- -1 aliphatic carbonates Chemical class 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- 239000004584 polyacrylic acid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000006138 lithiation reaction Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001913 cellulose Chemical class 0.000 description 3
- 229920002678 cellulose Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000005677 organic carbonates Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- YKGBNAGNNUEZQC-UHFFFAOYSA-N 6-methyl-n,n-bis(6-methylheptyl)heptan-1-amine Chemical compound CC(C)CCCCCN(CCCCCC(C)C)CCCCCC(C)C YKGBNAGNNUEZQC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910015892 BF 4 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- QTRBPWPVLFLELJ-UHFFFAOYSA-N F[Si](C(CC#N)C)(C)C Chemical compound F[Si](C(CC#N)C)(C)C QTRBPWPVLFLELJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012424 LiSO 3 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010041662 Splinter Diseases 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 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
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002996 emotional effect Effects 0.000 description 1
- 125000005912 ethyl carbonate group Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 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
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Chemical class 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
-
- 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
Definitions
- the invention relates to lithium-ion batteries containing an anode containing silicon particles, as well as organic or inorganic nitrates or nitrites, and processes for producing the lithium-ion batteries.
- Rechargeable lithium-ion batteries are today the most practical electrochemical energy storage devices with the highest gravimetric energy densities of, for example, up to 250 Wh / kg.
- Graphitic carbon is widely used as an active material for the negative electrode ("anode").
- the electrochemical capacity of graphite is at most a theoretical 372 mAh / g.
- Silicon is recommended as the anode active material with a higher electrochemical capacity.
- silicon experiences a volume change of up to 300% when lithium is stored and removed. As a result, the silicon particles are mechanically strongly stressed, which can ultimately lead to their breaking apart. This process is also known as electrochemical grinding and leads to a loss of electrical contacting of the active material in the electrode and thus to a loss of capacity of the electrode.
- SEI electrostatic senor
- Such an SEI is formed on the one hand when lithium-ion batteries containing silicon are charged for the first time, which causes initial capacity losses.
- volume changes of the silicon particles occur with each charge or discharge cycle, which exposes fresh silicon surfaces, which in turn react with constituents of the electrolyte and thereby form further SEI. This also leads to an immobilization of lithium and thus to a continuous, irreversible loss of capacity.
- Lithium-ion batteries in the electrolyte often contain cyclic / aliphatic carbonates as the main component, for example the methyl or ethyl carbonates mentioned in US Pat. No. 7,476,469.
- film-forming additives such as vinylene carbonate (VC) are typically added to the electrolyte in order to increase the performance of the cells.
- fluoroethylene carbonate (FEC) is often added to the electrolyte in order to stabilize the SEI against the change in volume of the silicon active material during charging and discharging of the lithium-ion battery.
- US2017033404, US20180062201, WO2017 / EP080808 (application number) or WO 2018/065046 also teach the use of electrolyte additives, such as nitrates.
- DE 102013210631 teaches adding fluorine-containing cyclic carbonates to the electrolyte in addition to lithium nitrate.
- US2014170478 and JP2005197175 deal with batteries which contain lithium metal as anodes. In order to suppress the formation of lithium dendrites on the surface of the lithium metal, compounds containing nitrogen, such as inorganic nitrate salts, are added to the battery. However, the anodes of US2014170478 and JP2005197175 do not contain any silicon particles. Lithium metal anodes and anodes containing silicon particles are technologically associated with completely different problems. US2002094480 recommends nitrite as an additive for anodes containing alkali metal (alloys).
- US2006222944 describes lithium-ion batteries with silicon (alloys) as anode active material, which is applied directly to the arrester as a thin film, and recommends the addition of various additives such as nitrates for this purpose.
- the anode active material of US2006222944 only has considerably limited contact with the electrolyte, so that such approaches cannot be compared with anode coatings in which silicon particles are embedded.
- WO17047030 describes the introduction of lithium nitrate into the cell by means of electrolysis Nitrate-containing electrolytes.
- the negative electrodes of WO17047030 contain lithium-containing silicon compounds with SiOx (0.5 x £ 1.6).
- the task was to provide lithium-ion batteries with anodes containing silicon particles, which have a high initial reversible capacity and, in the subsequent cycles, a stable electrochemical behavior with the smallest possible decrease in the reversible capacity (fading).
- the invention relates to lithium-ion batteries comprising cathode, anode, separator and electrolyte and a battery housing that accommodates the aforementioned components, characterized in that
- a cathode, an anode, a separator or some other reservoir located in the battery housing and different from the electrolyte contains one or more organic or inorganic nitrates or one or more organic or inorganic nitrites and
- the anode contains silicon particles with a silicon content of 3 90% by weight, based on the total weight of the silicon particles.
- Another object of the invention are methods for the production of lithium-ion batteries comprising cathode, anode, separator and electrolyte and a battery housing containing the aforementioned components, characterized in that one or more organic or inorganic nitrates or one or more organic or inorganic nitrites are introduced into a cathode, into an anode, into a separator or into another reservoir located in the battery housing and different from the electrolyte, and
- silicon particles with a silicon content of 3 90% by weight are used.
- the other reservoir which is located in the battery housing and is different from the electrolyte, is also referred to below for short as the other reservoir.
- the silicon particles with a silicon content of 3 90% by weight are also abbreviated as silicon particles in the following.
- the organic or inorganic nitrates or organic or inorganic nitrites are also referred to below for abbreviated form R / M-NO x compounds.
- the organic nitrates and / or the organic nitrites can be present, for example, as esters of nitric acid or as esters of nitric acid.
- esters are generally esters of nitric acid or nitric acid with aromatic or, in particular, aliphatic, optionally substituted or unsubstituted, alcohols having preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms and most preferably 1 to 5 Carbon atoms.
- substituents are halogen, hydroxy, alkoxy, aryloxy, carboxy or optionally substituted amine groups.
- Preferred esters of nitric acid are propyl nitrate and butyl nitrate, in particular isopropyl nitrate and isobutyl nitrate.
- Preferred esters of nitrous acid are methyl nitrite, ethyl nitrite, propyl nitrite and butyl nitrite, in particular isopropyl nitrite, isobutyl nitrite, t-butyl nitrite, benzyl nitrite and phenyl nitrite. Esters of nitrous acid are particularly preferred.
- Preferred R / M-NO x compounds are inorganic nitrites and, in particular, inorganic nitrates.
- the inorganic nitrates and / or inorganic nitrites are preferably in the form of their salts, particularly preferably in the form of their (earth) alkali or ammonium salts and most preferably in the form of their alkali salts.
- Corresponding ammonium salts contain, for example, tetraalkyl or tetraaryl ammonium compounds, the alkyl or aryl radicals of which can optionally be substituted or unsubstituted and preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms and most preferably 1 to 5 Have carbon atoms.
- substituents are halogen, hydroxyl, alkoxy, aryloxy or, if appropriate, substituted amine groups.
- Examples of such Salts are tetrabutylammonium, tetraethylammonium or tetrapropylammonium salts of nitrate or nitrite.
- Preferred alkali salts are sodium nitrite, potassium nitrite and, in particular, lithium nitrite. Particularly preferred alkali salts are sodium nitrate, potassium nitrate and lithium nitrate. The most preferred R / M-NO x compound is lithium nitrate.
- the anode, the cathode and / or the separator preferably contain 0.01 to 5.0 mg / cm 2 , particularly preferably 0.02 to 2.0 mg / cm 2 and most preferably 0.1 to 1.5 mg / cm 2 of R / M-NO x compounds, each based on the area of the anode, the cathode and / or the separator.
- the anode, the cathode and / or the separator preferably contain 0.14 to 73.0 mmol / cm 2 , particularly preferably 0.29 to 29.0 mmol / cm 2 and most preferably 1.45 to 21.75 mmol / cm 2 of R / M-NO x compounds, each based on the area of the anode, the cathode and / or the separator.
- the anode, the cathode and the separator contain a total of preferably 0.5 to 60% by weight, particularly preferably 1 to 40% by weight and most preferably 4 to 20% by weight of R / M-NO x -Ver - Bonds, based on the total dry weight of the anode coating, the cathode coating and the separator.
- the anode, the cathode or the separator preferably contain 0.5 to 60% by weight, particularly preferably 1 to 40% by weight and most preferably 4 to 20% by weight of R / M-NO x - Links.
- these data relate to the dry weight of the anode coating, in the case of the cathode to the dry weight of the cathode coating and in the case of the separator to the dry weight of the separator.
- the cathode, the anode and / or the separator contain R / M-NO x compounds in an amount that is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5.0% by weight and am most preferably 0.1 to 2.5% by weight, based on the weight of the electrolyte.
- the R / M-NO x compounds are generally poorly soluble in the electrolyte.
- the solubility of the R / M-NO x compounds in the electrolyte under normal conditions according to DIN 50014 (23/50) is preferably ⁇ 2% by weight, particularly preferably 1% by weight and most preferably 0.5% by weight. -%.
- the R / M-NO x compounds can be applied to the cathode, the anode and / or the separator in the form of a film or in the form of a coating.
- the R / M-NO X connections can also be part of the cathode or anode coating or be incorporated into the separator.
- the R / M-NO x compounds can be introduced into the cathode, the anode or the separator, for example by applying one or more solutions containing R / M-NO x compounds to the cathode, the anode or the separator and then dried.
- the application can take place, for example, by spraying or by impregnation or dripping.
- the cathode, the anode or the separator can be immersed in appropriate solutions. The common devices and procedures can be used for this.
- the R / M-NO x compounds are applied at temperatures of preferably 10 to 120 ° C, particularly preferably 15 to 80 ° C and most preferably 20 to 30 ° C.
- the solutions of the R / M-NO x compounds, the anodes, the cathodes and / or the separators can have the aforementioned temperatures.
- the solutions of the R / M-NO x compounds can contain one or more solvents.
- solvents are water or organic solvents such as alcohols, ethers or esters, in particular ethanol, tetrahydrofuran, glyme, dimethyl ether or 1,3-dioxalane.
- Solvent mixtures containing water and one or more organic solvents, in particular alcohols, are preferred. Such solvent mixtures preferably hold 3 50% by weight and particularly preferably 3 80% by weight water, based on the total weight of the solvent mixture.
- the use of water or alcohols as the exclusive solvent is also preferred.
- the solutions preferably contain R / M-NO x compounds of preferably 1 to 700 mg, in particular 10 to 500 mg per milliliter of solvent.
- the solvent is preferably selected so that the R / M-NO x compounds are completely dissolved in the solvent.
- drying can take place, for example, at temperatures of 30 to 120 ° C, in particular 50 to 120 ° C. If necessary, the drying can be carried out under reduced pressure. Underpressure generally means a lower pressure than ambient pressure. Continuous or batch processes are generally suitable for drying. The drying can be carried out, for example, over a period of 1 minute to 24 hours, preferably 1 minute to 12 hours and more preferably 1 minute to 1 hour.
- the R / M-NO x compounds can also be used as an additional component in the production of the anodes, cathodes or separators, for example part of the anode coating agent, cathode coating agent or separator formulation for the manufacturer - the anodes, cathodes or separators.
- the other reservoir can be attached, for example, on the inside, in particular directly on the inside of the battery housing.
- the inside is the side of the battery housing that is oriented towards the cathode, anode and the separator of the lithium-ion battery.
- the other reservoir contains R / M-NO x compounds in an amount which is preferably 0.01 and 10% by weight, particularly preferably 0.02 to 5% by weight and most preferably 0.05 to 2.5 % By weight, based on the total weight of the electrolyte.
- the inside of the battery housing can have a coating that contains R / M-NO x compounds.
- the coating can be based, for example, on one or more R / M-NOx compounds and optionally one or more further components, such as adhesion promoters or, in particular, polymers.
- the polymers which are mentioned below as binders for the anode materials or for the cathode materials are preferred. Polymethyl (meth) acrylate, poly (meth) acrylic acid (salts) or styrene-butadiene copolymers are particularly preferred.
- Silanes for example, can be used as adhesion promoters.
- a coating preferably contains 0 to 60% by weight, in particular 1 to 50% by weight, of further constituents, in particular polymers.
- a coating preferably contains 40 to 100% by weight, in particular 50 to 99% by weight.
- -% of R / M-NO x compounds The data in% by weight relate in each case to the dry weight of the coating.
- the coating has a layer thickness of preferably 0.5 to 5 mm, particularly preferably 0.5 to 3 mm and most preferably 0.5 to 2 mm.
- the coating can be obtained, for example, by applying a solution containing R / M-NO x compounds directly to the inside of the battery housing or to a polymer-coated inside of the battery housing.
- the solutions preferably contain the further constituents, in particular the polymers, at a concentration of preferably 0.1 to 20% by weight, based on the total weight of the solvents.
- the solutions can be applied, for example, by spraying, impregnating or dipping.
- the coating can be carried out as described above for the cathode, the anode or the separator, in particular with regard to solvents, temperatures or drying.
- another reservoir can be a porous carrier, for example in the form of a carrier of cushions, fibers, textile structures, films or foils, the R / M-NO x compounds and optionally one or more other components, such as adhesion promoters or especially polymers.
- Textile structures can be woven or non-woven.
- the porous support can be based, for example, on materials that are also customary for separators. Examples of materials for the porous carrier are glass fibers, polyester, Teflon, polyethylene, polypropylene or polytetrafluoroethylene (PTFE).
- the porous carrier can, for example, line the inside of the battery housing or be introduced into the lithium-ion battery as an additional winding around the cell stack or as an additional chamber, in particular in the case of a laminated thin-film housing.
- the R / M-NO x compounds can be applied to the porous support, for example by means of spraying, impregnation or immersion. This can be done, for example, as described above for the cathode, the anode or the separator.
- the porous support contains R / M-NO x compounds at preferably 0.01 to 5.0 mg / cm 2 , particularly preferably 0.02 to 2.0 mg / cm 2 and most preferably 0.05 to 1.5 mg / cm 2 , based on the area of the porous support.
- the porous support contains R / M-NO x compounds at preferably 0.14 to 73.0 mmol / cm 2 , particularly preferably 0.29 to 29.0 mmol / cm 2 and most preferably 0.72 to 21.75 mmol / cm 2 , based on the area of the porous support.
- the other reservoir is generally in contact with the electrolyte like the anode, the cathode or the separator in conventional batteries.
- the anode material contains silicon particles.
- the volume-weighted particle size distribution of Siliciumpar- Tikel is preferably between the diameter-percentiles d 3 10 0.2 mm and d 90 £ 20.0 mm, more preferably between d 10 mm and d 3 0.2 90 £ 10.0 mm, and most preferably between d 10 3 0.2 mm to d 90 £ 5.0 mm.
- the silicon particles have a volume-weighted particle size distribution with diameter percentiles d 10 of preferably £ 10 mm, particularly preferably £ 5 mm, even more preferably £ 3 mm and most preferably £ 1 mm.
- the silicon particles have a volume-weighted particle size distribution with diameter percentiles d 90 of preferably 3 0.5 mm. In one embodiment of the present invention, the aforementioned d 90 value is preferably 3 5 mm.
- the volume-weighted particle size distribution of the silicon particles has a width d 90 -d 10 of preferably £ 15.0 mm, more preferably £ 12.0 mm, even more preferably £ 10.0 mm, particularly preferably £ 8.0 mm and most preferably £ 4.0mm.
- the volume-weighted particle size distribution of the silicon particles has a width d 90 -d 10 of preferably 3 0.6 mm, particularly preferably 3 0.8 mm and most preferably 3 1.0 mm.
- the volume-weighted particle size distribution of the silicon particles has diameter percentiles d 90 of preferably 0.5 to 10.0 mm, particularly preferably 0.6 to 7.0 mm, even more preferably 2.0 to 6.0 mm and am most preferably 0.7 to 3.0 mm.
- silicon particles are also preferred whose volume-weighted particle size distribution has diameter percentiles d 50 of 10 to 500 nm, particularly preferably 20 to 300 nm, even more preferably 30 to 200 nm and most preferably 40 to 100 nm.
- the volume-weighted particle size distribution of the silicon particles can be determined by static laser scattering using the Mie model with the Horiba LA 950 measuring device with ethanol as the dispersing medium for the silicon particles.
- the silicon particles are preferably not aggregated, preferably not agglomerated and / or preferably not nano-structured.
- Aggregated means that several spherical or largely spherical primary particles, such as those initially formed in the production of silicon particles by means of gas phase processes, grow together, melt or sinter together to form aggregates. In the case of aggregates, it is therefore a matter of a particle that comprises several primary particles.
- Aggregates can form agglomerates. Agglomerates are loosely clusters of aggregates.
- Agglomerates can typically easily be broken down into aggregates again using kneading or dispersing processes. Such processes cannot completely break down aggregates into the primary particles. Because of their formation, aggregates and agglomerates inevitably have completely different sphericities and grain shapes than the silicon particles according to the invention. The presence of silicon particles in the form of aggregates or agglomerates can be made visible, for example, by means of conventional scanning electron microscopy (SEM). Static light scattering methods for determining the particle size distributions or particle diameters of silicon particles, on the other hand, cannot differentiate between aggregates and agglomerates.
- SEM scanning electron microscopy
- Non-nanostructured silicon particles generally have characteristic BET surfaces.
- the BET surface areas of the silicon particles are preferably 0.01 to 30.0 m 2 / g, more preferably 0.1 to 25.0 m 2 / g, particularly preferably 0.2 to 20.0 m 2 / g and most preferably 0.2 to 18.0 m 2 / g.
- the BET surface area is determined in accordance with DIN 66131 (with nitrogen).
- the silicon particles have a sphericity of preferably 0.3 £ Y £ 0.9, particularly preferably 0.5 £ Y £ 0.85 and most preferably 0.65 £ Y £ 0.85. Silicon particles with such sphericalities become accessible in particular through production by means of grinding processes.
- the sphericity Y is the ratio of the surface of a sphere of equal volume to the actual surface of a body (definition by Wadell). Spherical cities can be determined from conventional SEM images, for example.
- the silicon particles have a silicon content of preferably 395% by weight, particularly preferably 98% by weight and most preferably 99% by weight, based on the total weight of the silicon particles.
- the silicon particles are preferred.
- the silicon particles are preferably based on elemental silicon.
- Elemental silicon can be high-purity silicon or silicon from metallurgical processing which, for example, can contain elemental impurities such as Fe, Al, Ca, Cu, Zr, C.
- the silicon particles can optionally be doped with foreign atoms (such as B, P, As). Such foreign atoms are generally only contained in small amounts.
- the silicon particles can contain silicon oxide, in particular on the surface of the silicon particles. If the silicon particles contain a silicon oxide, then the stoichiometry of the oxide SiO x is preferably in the range 0 ⁇ x ⁇ 1.3.
- the layer thickness of silicon oxide on the surface of the silicon particles is preferably less than 10 nm.
- the silicon particles have an oxygen content of preferably £ 5% by weight, particularly preferably £ 3% by weight and most preferably £ 1% by weight. %, based on the total weight of the silicon particles.
- the surface of the silicon particles can optionally be covered by an oxide layer or by other inorganic and organic groups.
- Particularly preferred silicon particles have Si — OH or Si — H groups or covalently bonded organic groups, such as alcohols or alkenes, on the surface.
- the silicon particles are preferably not in the form of alloys M y Si.
- M can be, for example, metals or semi-metals, such as alkali metals, Sn, Al, B, Mg, Ca, Ag or Zn.
- the silicon particles can be produced, for example, by grinding processes. Dry or wet grinding processes, for example, as described in DE-A 102015215415, for example, come into consideration as grinding processes.
- the anode material generally comprises silicon particles, one or more binders, optionally organic or inorganic nitrates, optionally organic or inorganic nitrites, optionally graphite, optionally one or more further electrically conductive components and optionally one or more additives.
- the silicon content in the anode material is preferably 40 to 95% by weight, particularly preferably 50 to 90% by weight and most preferably 60 to 80% by weight, based on the total weight of the anode material.
- Preferred binders are polyacrylic acid or its alkali salts, in particular lithium or sodium salts, polyvinyl alcohols, cellulose or cellulose derivatives, polyvinylidene fluoride, polytetrafluoroethylene, polyolefins, polyimides, in particular polyamide imides, or thermoplastic elastomers, in particular ethylene-propylene-diene Terpolymers.
- Polyacrylic acid, polymethacrylic acid or cellulose derivatives, in particular carboxymethyl cellulose are particularly preferred.
- the alkali salts, in particular lithium or sodium salts, of the abovementioned binders are also particularly preferred.
- the alkali salts in particular lithium or sodium salts, of polyacrylic acid or polymethacrylic acid. All or preferably some of the acid groups of a binder can be present in the form of salts.
- the binders have a molar mass of preferably 100,000 to 1,000,000 g / mol. Mixtures of two or more binders can also be used.
- Generally natural or synthetic graphite can be used as graphite.
- the graphite particles preferably have a volume-weighted particle size distribution between the diameter percentiles d 10 > 0.2 mm and d 90 ⁇ 200 mm.
- Preferred further electrically conductive components are carbon black, carbon nanotubes or metallic particles, for example copper.
- Amorphous carbon is also preferred, in particular hard carbon or soft carbon.
- Amorphous carbon is known to be non-graphitic.
- the anode material preferably contains 0 to 40% by weight, particularly preferably 0 to 30% by weight and most preferably 0 to 20% by weight of further electrically conductive components, based on the total weight of the anode material.
- anode material additives examples include pore formers, dispersants, leveling agents or dopants, for example elemental lithium.
- Preferred formulations for the anode material of the lithium-ion batteries preferably contain 5 to 95% by weight, in particular 60 to 85% by weight, silicon particles; 0 to 40% by weight, in particular 0 to 20% by weight, of further electrically conductive components 0 to 80% by weight, in particular 5 to 30% by weight, graphite; 0 to 25% by weight, in particular 5 to 15% by weight, of binder; and optionally 0 to 80% by weight, in particular 0.1 to 5% by weight, of additives; where the data in% by weight relate to the total weight of the anode material and the proportions of all components of the anode material add up to 100% by weight.
- the proportion of graphite particles and / or other electrically conductive components is at least 10% by weight in total, based on the total weight of the anode material.
- the processing of the components of the anode material to an anode ink or paste can, for example, in a solvent such as water, hexane, toluene, tetrahydrofuran, N-methyl- pyrrolidone, N-ethylpyrrolidone, acetone, ethyl acetate, dimethyl sulfoxide, dimethylacetamide or ethanol, or solvent mixtures, preferably using rotor-stator machines, high-energy mills, planetary kneaders, agitator ball mills, vibrating plates or ultrasonic devices.
- a solvent such as water, hexane, toluene, tetrahydrofuran, N-methyl- pyrrolidone, N-ethylpyrrolidone, acetone, ethyl acetate, dimethyl sulfoxide, dimethylacetamide or ethanol, or solvent mixtures, preferably using rotor-stator
- the anode ink or paste has a pH value of preferably 2 to 7.5 (determined at 20 ° C., for example with the WTW pH 340i pH meter with SenTix RJD probe).
- the anode ink or paste can, for example, be applied to a copper foil or another current collector, as described, for example, in WO 2015/117838.
- the layer thickness that is to say the dry layer thickness of the anode coating, is preferably from 2 mm to 500 mm, particularly preferably from 10 mm to 300 mm.
- the cathode material preferably comprises cathode active materials, binders, optionally organic or inorganic nitrates, optionally organic or inorganic nitrites, optionally electrically conductive components and optionally additives.
- Preferred cathode active materials are lithium cobalt oxide, lithium nickel oxide, lithium nickel cobalt oxide (doped or undoped), lithium manganese oxide (spinel), lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium iron phosphate, lithium cobalt aluminum phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium vanadium phosphate, lithium vanadium phosphate, lithium vanadium phosphate, lithium vanadium phosphate, lithium vanadium phosphate.
- the corresponding components described above for the anode material or the components described for this in US2014 / 0170478 can be used as binders, electrically conductive components and additives.
- the cathode can be produced in a conventional manner, for example as specified in US2014 / 0170478 or analogously to the anode production described above.
- the separator is generally based on an electrically insulating membrane that is permeable to ions, as is commonly used in battery manufacture. As is known, the separator separates the anode from the cathode and thus prevents electronically conductive connections between the electrodes (short circuit).
- the separator can, for example, be based on polyolefins such as polyethylenes or polypropylenes, silicones, glass fiber filter papers, ceramic materials such as silicon oxides, aluminum oxides or their mixed oxides, or microporous xerogel layers such as microporous pseudo-boehmite layers, and optionally organic or contain inorganic nitrates or optionally organic or inorganic nitrites.
- polyolefins such as polyethylenes or polypropylenes, silicones, glass fiber filter papers, ceramic materials such as silicon oxides, aluminum oxides or their mixed oxides, or microporous xerogel layers such as microporous pseudo-boehmite layers, and optionally organic or contain inorganic nitrates or optionally organic or inorganic nitrites.
- the electrolytes contain, for example, aprotic solvents, optionally lithium-containing conductive salts, optionally film-forming agents and optionally additives.
- Lithium-containing conductive salts are preferably selected from the group comprising LiPF 6 , L BF 4 , LiClO 4 , LiAsF 6 , (LiB (C 2 O 4 ) 2 , LiBF 2 (C 2 O 4 )), LiC (SO 2 C x F 2x +1 ) 3 , LiN (SO 2 C x F 2x + 1 ) 2 , and
- LiSO 3 C x F 2x + where x assumes integer values from 0 to 8, and mixtures thereof.
- the lithium-containing conductive salts are contained in the electrolyte in an amount of preferably 3 1% by weight, particularly preferably 1 to 20% by weight, and most preferably 10 to 15% by weight, based on the total weight of the electrolyte.
- the aprotic solvent is preferably selected from the group comprising organic carbonates, such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, vinyl carbonate, propylene carbonate, butylene carbonate; cyclic and linear esters, such as methyl acetate, ethyl acetate, butyl acetate, propyl propionate, ethyl butyrate, ethyl isobutyrate; cyclic and linear ethers, such as 2-methyltetrahydrofuran, 1,2-diethoxymethane, THF, dioxane, 1,3-dioxolane, diisopropyl ether, diethylene glycol dimethyl ether, ketones, such as cyclopentanone, diisopropyl ketone, methyl isobutyl ketone; Lactones such as g-butyrolactone; Sulfolane, di- methyl sulfoxide, form
- film formers are vinylene carbonate, ethylene carbonate and especially fluoroethylene carbonate.
- the electrolyte preferably contains up to 10% by weight, particularly preferably 0.1 to 5% by weight and even more preferably 0.5 to 3% by weight of film-forming agent, based on the total weight of the electrolyte.
- the cycle behavior of lithium-ion batteries can be further improved by adding a film former to the electrolyte.
- electrolyte additives examples include organic isocyanates, for example to reduce the water content, HF scavengers, solubilizers for LiF, organic lithium salts, inorganic lithium salts, complex salts, amines such as tributylamine, tripentylamine, trihexylamine or triisooctylamine, and / or nit - Rile, such as caproonitrile, valeronitrile or 3- (fluoro-dimethylsilyl) -butane-nitrile.
- the electrolyte which is introduced into the lithium-ion battery preferably contains no organic or inorganic nitrates according to the invention and / or no organic or inorganic nitrites according to the invention.
- the cathode, the anode, the separator, the electrolyte and other components such as the battery housing can be built into a lithium-ion battery in a conventional manner, as described, for example, in US9831527, US2011014518 or WO 2015/117838. Unless otherwise stated, conventional starting materials and processes can be used.
- the lithium-ion batteries according to the invention can be produced in all customary forms, for example in wound, folded or stacked form.
- the anode material, in particular the silicon particles, is preferably only partially lithiated in the fully charged lithium-ion battery. Fully charged refers to the state of the battery in which the anode material of the battery has its highest lithium load.
- Partial lithiation of the anode material means that the maximum lithium absorption capacity of the silicon particles in the anode material is not exhausted.
- the maximum lithium absorption capacity of the silicon particles generally corresponds to the formula Li 4.4 Si and is thus 4.4 lithium atoms per silicon atom. This corresponds to a maximum specific capacity of 4200 mAh per gram of silicon.
- the ratio of the lithium atoms to the silicon atoms in the anode of a lithium-ion battery can be adjusted, for example, via the electrical charge flow.
- the degree of lithiation of the anode material or of the silicon particles contained in the anode material is proportional to the electrical charge that has flowed. With this variant, the capacity of the anode material for lithium is not fully utilized when charging the lithium-ion battery. This results in a partial lithiation of the anode.
- the Li / Si ratio of a lithium-ion battery is set by cell balancing.
- the lithium-ion batteries are designed in such a way that the lithium absorption capacity of the anode is preferably greater than the lithium output capacity of the cathode. This means that in the fully charged battery the lithium absorption capacity of the anode is not fully exhausted, i.e. that the anode material is only partially lithiated.
- the Li / Si ratio in the anode material in the fully charged state of the lithium-ion battery is preferably £ 2.2, particularly preferably £ 1.98 and most preferably £ 1.76.
- the Li / Si ratio in the anode material in the fully charged state of the lithium-ion battery is preferably 3 0.22, particularly preferably 3 0.44 and most preferably 3 0.66.
- the capacity of the silicon of the anode material of the lithium-ion battery is preferably used to the extent of £ 50%, particularly preferably to £ 45% and most preferably to £ 40%, based on a capacity of 4200 mAh per gram of silicon.
- the degree of lithiation of silicon or the utilization of the capacity of silicon for lithium can be determined, for example, as described in WO2017 / 025346 on page 11, line 4 to page 12, line 25.
- the lithium-ion batteries according to the invention show an improved cycle behavior.
- the lithium-ion batteries have a slight irreversible loss of capacity in the first charging cycle and stable electrochemical behavior with only minor fading in the subsequent cycles.
- a lower initial capacity loss and in particular a lower continuous capacity loss of the lithium-ion batteries can be achieved.
- lithium-ion batteries according to the invention hardly suffer any signs of fatigue, for example as a result of mechanical destruction of the anode material or SEI.
- the cycling behavior of lithium-ion batteries can be further improved by adding a film former to the electrolyte.
- Film-forming agents and the inventive use of the nitrates or nitrites according to the invention work together here in a synergistic manner.
- the separator (glass fiber filter, glass fiber type A / E, Pall Corporation, thickness 330 mm, diameter 16 mm, porosity 95%) was dried at 80 ° C. in a drying cabinet and the weight was determined. 60 ml of the respective aqueous LiNO 3 solution (see Table 1) were applied to the separator with a measuring pipette and dried again at 80 ° C. and the weight was determined.
- the weight difference gave the amount of LiNO 3 applied to the separator and was expressed in mg LiNO 3 per cm 2 of separator area
- Lithium-ion batteries with the separators from Examples 1a-d Lithium-ion batteries with the separators from Examples 1a-d:
- a coating based on lithium-nickel-manganese-cobalt oxide 6: 2: 2 with a content of 94.0% and an average weight per unit area of 14.8 mg / cm 2 (obtained from Varta Microbatteries) was used as the working electrode or positive elect - rode (Dm 15 mm) used.
- the electrolyte used consisted of a 1.0 molar Solution of lithium hexafluorophosphate in a 1: 2 (v / v) mixture of ethylene carbonate and diethyl carbonate.
- the cell was built in a glove box ( ⁇ 1 ppm H 2 O, O 2 ); the dry matter content of all components used was below 20 ppm.
- the lithium-ion batteries were initially stored at 45 ° C. for 20 hours.
- the electrochemical testing was carried out at 23 ° C.
- the cell was charged using the cc / cv (constant current / constant voltage) method with a constant current of 15 mA / g (corresponds to C / 10) in the first cycle and of 75 mA / g (corresponds to C / 2 ) in the following cycles and after reaching the voltage limit of 4.2 V with constant voltage until the current falls below 1.5 mA / g (corresponds to C / 100) or 19 mA / g (corresponds to C / 8).
- the cell was discharged using the cc (constant current) method with a constant current of 15 mA / g (corresponds to C / 10) in the first cycle and of 75 mA / g (corresponds to C / 2) in the subsequent cycles until it was reached the voltage limit of 3.0 V.
- the selected specific current related to the weight of the coating on the positive electrode. The test results are summarized in Table 5.
- Impregnation of an anode containing Si with LiNO 3 Impregnation of an anode containing Si with LiNO 3 :
- Si-containing anode (70% by weight silicon, 25% by weight graphite, 5.0% by weight polyacrylic acid (binder)) with an average coating weight per unit area of 3.01 mg / cm 2 and a diameter of 15 mm was impregnated with 30 ml of an ethanolic LiNO 3 solution (see Table 2).
- the impregnated anodes were then dried at 80 ° C. for 2 hours in a drying cabinet and the weight was determined.
- the amount of LiNO 3 applied to the anode was calculated from the difference in weight and stated in mg LiNO 3 per cm 2 of anode area (mg / cm 2 of anode ) (see Table 2).
- Lithium-ion batteries with the anodes from Example 4a-b Lithium-ion batteries with the anodes from Example 4a-b:
- the impregnated cathodes were then dried in a drying cabinet at 80 ° C. for 2 hours and the weight was determined.
- the amount of LiNO 3 applied to the cathode was calculated from the weight difference and stated in mg LiNO 3 per cm 2 cathode area (mg / cm 2 cathode ) (see Table 3).
- the dispersion was applied to a copper foil with a thickness of 0.030 mm (Schlenk metal foils, SE-Cu58) using a film frame with a gap height of 0.08 mm (Erichsen, model 360).
- the anode coating produced in this way was then predried at 50 ° C. and dried in a drying cabinet at 80 ° C. and 1 bar air pressure for 2 h.
- the average weight per unit area of the dry anode coating was 3.37 mg / cm 2 with a nitrate content of 0.34 mg / cm 2 (10% by weight LiNO 3 in the solids content of the anode coating).
- the coating density was 1.15 g / cm 3 .
- Lithium-ion battery with nitrate-free anode, cathode and separator Lithium-ion battery with nitrate-free anode, cathode and separator.
- the electrolyte used consisted of a 1.0 molar solution of lithium hexafluorophosphate in a 1: 2 (v / v) mixture of ethylene carbonate and diethyl carbonate and optionally LiNO 3 (see Table 4).
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CN115632124B (zh) * | 2022-12-22 | 2023-04-14 | 宜宾锂宝新材料有限公司 | 一种高镍三元正极材料、其制备方法及锂离子电池 |
WO2024144171A1 (ko) * | 2022-12-26 | 2024-07-04 | 주식회사 엘지에너지솔루션 | 음극 조성물, 이의 제조 방법, 음극 슬러리, 음극 및 리튬 이차 전지 |
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CA1179291A (en) | 1981-10-30 | 1984-12-11 | David T. Ahlberg | Distillation apparatus |
KR100545613B1 (ko) | 2001-01-18 | 2006-01-25 | 산요덴키가부시키가이샤 | 리튬 이차 전지 |
US6528207B2 (en) | 2001-01-18 | 2003-03-04 | Wilson Greatbatch Ltd. | Electrochemical cell having an electrode with a nitrite additive in the electrode active mixture |
JP2005197175A (ja) | 2004-01-09 | 2005-07-21 | Sony Corp | 正極、負極、電解質および電池 |
US7923148B2 (en) | 2005-03-31 | 2011-04-12 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery including a negative electrode containing silicon and an additive which retards oxidation of silicon during battery operation |
JP5515476B2 (ja) | 2009-07-16 | 2014-06-11 | ソニー株式会社 | 二次電池、負極、正極および電解質 |
JP5346839B2 (ja) * | 2010-02-15 | 2013-11-20 | シャープ株式会社 | リチウムイオン二次電池 |
US9577289B2 (en) | 2012-12-17 | 2017-02-21 | Sion Power Corporation | Lithium-ion electrochemical cell, components thereof, and methods of making and using same |
DE102013210631A1 (de) | 2013-06-07 | 2014-12-11 | Volkswagen Aktiengesellschaft | Neue Elektrolytzusammensetzung für Hochenergieanoden |
KR101749186B1 (ko) | 2013-09-11 | 2017-07-03 | 삼성에스디아이 주식회사 | 리튬 전지용 전해질, 이를 포함하는 리튬 전지, 및 리튬 전지용 전해질의 제조방법 |
DE102014202156A1 (de) | 2014-02-06 | 2015-08-06 | Wacker Chemie Ag | Si/G/C-Komposite für Lithium-Ionen-Batterien |
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DE102015215415A1 (de) | 2015-08-12 | 2017-02-16 | Wacker Chemie Ag | Siliciumpartikel enthaltende Anodenmaterialien für Lithium-Ionen-Batterien |
JP6360022B2 (ja) | 2015-09-16 | 2018-07-18 | 信越化学工業株式会社 | 非水電解質二次電池用負極活物質の製造方法、及び非水電解質二次電池の製造方法 |
US10128537B2 (en) * | 2016-08-30 | 2018-11-13 | Wildcat Discovery Technologies, Inc. | Electrolyte formulations for electrochemical cells containing a silicon electrode |
CN109792041A (zh) * | 2016-10-05 | 2019-05-21 | 瓦克化学股份公司 | 锂离子电池 |
US11121353B2 (en) * | 2019-03-18 | 2021-09-14 | Chongqing Jinkang New Energy Automobile Co., Ltd. | Systems and methods for potassium enhancing silicon-containing anodes for improved cyclability |
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