CN114551829A - Cathode material and lithium ion battery containing same - Google Patents
Cathode material and lithium ion battery containing same Download PDFInfo
- Publication number
- CN114551829A CN114551829A CN202210126300.9A CN202210126300A CN114551829A CN 114551829 A CN114551829 A CN 114551829A CN 202210126300 A CN202210126300 A CN 202210126300A CN 114551829 A CN114551829 A CN 114551829A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- graphite
- electrode material
- anode
- capacity
- 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 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 239000010406 cathode material Substances 0.000 title description 10
- 239000007773 negative electrode material Substances 0.000 claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 57
- 239000010439 graphite Substances 0.000 claims abstract description 57
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims description 26
- 238000012360 testing method Methods 0.000 claims description 23
- 238000004435 EPR spectroscopy Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- -1 aromatic ring compound Chemical class 0.000 claims description 13
- 238000001237 Raman spectrum Methods 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000006183 anode active material Substances 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001069 Raman spectroscopy Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 37
- 229910052744 lithium Inorganic materials 0.000 description 37
- 239000013067 intermediate product Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 10
- 239000011267 electrode slurry Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229910021383 artificial graphite Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910021385 hard carbon Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 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 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000417 polynaphthalene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 description 2
- 229910010088 LiAlO4 Inorganic materials 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003273 ketjen black Substances 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
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
Abstract
The invention discloses a negative electrode material and a lithium ion battery containing the same. On one hand, the gram capacity of the graphite can be improved by coating the graphite with the product of high-temperature carbonization of the aromatic polymer, the carbon structure of which has the ordered degree between that of the graphite and the amorphous carbon; on the other hand, the high-temperature cycle capacity retention rate of the lithium ion battery can be improved by constructing the strong interaction of the graphite surface unsaturated bond and the aromatic polymer conjugated pi bond.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a negative electrode material and a lithium ion battery containing the same.
Background
At present, the cathode material of a commercial lithium ion battery is mainly graphite, the preparation process is mature, but the theoretical gram capacity is only 372mAh/g, and the development requirement of the next generation of high energy density lithium ion battery cannot be met.
Compared with graphite, the amorphous carbon has abundant micropores and can accommodate more lithium ions, and the gram volume of the material can be improved to a certain extent by coating the graphite with the amorphous carbon. However, the specific surface area of amorphous carbon is large, and when the content thereof is too large, side reactions of the electrolyte solution on the surface thereof increase at high temperatures, and the battery capacity is rapidly degraded with cycles.
Therefore, how to construct an anode material which has high gram capacity and capacity retention rate superior to that of graphite in high-temperature cycle becomes a difficult problem to be solved urgently in the field of anode material development and battery design.
Disclosure of Invention
In order to improve the technical problem, the invention provides the following technical scheme:
a negative electrode material comprising graphite and a coating on at least a portion of a surface of the graphite; the anode material has at least one of the following characteristics:
1) in the Raman spectrum test, the Raman shift is 1300-1400cm-1、1550-1650cm-1The region has a height of I1、I2Characteristic peak of (1), and 0.3 < I1/I2＜0.6；
2) The negative electrode material has a resonance signal in an Electron Paramagnetic Resonance (EPR) test.
According to the invention, the coating is a high-temperature carbonized product of an aromatic polymer.
According to the invention, the aromatic polymer is chosen from homopolymers or copolymers of aromatic ring compounds. For example, the aromatic ring compound is selected from at least one of naphthalene, biphenyl, anthracene, phenanthrene, perylene, and pyrene.
Illustratively, the homopolymer is selected from at least one of polynaphthalene, polybiphenyl, polyanthrylene, polyphenanthrene, polyperylene, and polypyrene.
The copolymer may be a copolymer of two or more aromatic ring compounds, or a copolymer of at least one aromatic ring compound and another monomer; the other monomer is selected from olefin monomers, (meth) acrylic acid (ester) monomers, and the like; for example, the aromatic ring compound is selected from at least one of naphthalene, biphenyl, anthracene, phenanthrene, perylene, and pyrene.
According to the invention, the aromatic polymer has a number average molecular weight of 500 to 10000, illustratively 500, 1000, 2000, 5000, 8000, 10000 or any point within the range of two of the aforementioned values.
According to the invention, the degree of crystallinity (i.e. the degree of carbon structural order) of the coating is intermediate between that of graphite and amorphous carbon.
According to the invention, the specific surface area of the coating is lower than that of amorphous carbon, for example by at least 30m2G, also e.g. at least 40m lower2/g。
According to the invention, there is a bonding between the coating and the graphite. In the invention, a small amount of defect sites are produced on the surface of graphite by using a mechanical crushing method, so that unsaturated bonds are generated to form a bonding effect with conjugated pi bonds of an aromatic polymer, a graphite-cladding interface structure with high stability can be obtained, and the stronger the bonding effect of the cladding and the graphite, the better the protection effect on the graphite, and the higher the cycle stability of the prepared battery.
According to the invention, in the negative electrode material, the mass percentage of the coating is 1-22%.
According to the present invention, the high temperature carbonization product of the aromatic polymer refers to a product formed by subjecting the aromatic polymer to a high temperature carbonization treatment. Specifically, the high-temperature carbonization treatment may include a secondary calcination treatment; the first-stage calcination treatment is carried out at a temperature rise rate of 1-4 ℃/min, the temperature is raised to 200-300 ℃, and the temperature is kept for 1-3 h; and the temperature of the second-stage calcination treatment is raised to 600-800 ℃ at the temperature rise rate of 1-4 ℃/min, and the second-stage calcination treatment is kept for 2-5 hours.
According to the invention, the median particle diameter Dv50 of the negative electrode material is between 6.0 μm and 20.0 μm, exemplarily 6.0 μm, 10.0 μm, 15.0 μm, 20.0 μm or any point within the range of the aforementioned two-by-two numerical compositions.
According to the invention, the specific surface area BET of the negative electrode material is 0.5-6.5 m2G, exemplary 0.5m2/g、1.0m2/g、2.0m2/g、3.0m2/g、4.0m2/g、5.0m2/g、6.5m2Or any point in the range consisting of two of the foregoing values.
According to the invention, in a Raman spectrum test, the Raman shift of the cathode material is 1300-1400cm-1、1550～1650cm-1The region has a height of I1、I2Characteristic peak of (1), and 0.3 < I1/I2< 0.6, illustratively 0.35, 0.40, 0.45, 0.50, 0.55 or any point within the range of values consisting of two of the foregoing.
According to the invention, in a button half cell test, the capacity of the negative electrode material is Q when lithium is removed to 0.3V1With the capacity of 1.5V for delithiation being Q2Then Q is1And Q2Satisfies 0.1 < (Q)2-Q1)/Q2< 0.4, illustratively 0.15, 0.2, 0.25, 0.30, 0.35 or any point within the range consisting of two of the foregoing values.
In the present invention, the measurement of the graphite component in the negative electrode material is performed by an X-ray diffraction (XRD) method. For example, the test was carried out using Shimadzu XRD-6100X-ray diffractometer, using Cu K.alpha.ray as incident X-ray, 2 θ as abscissa and unit as DEG, signal intensity as ordinate, the test interval was 20 to 70 DEG, the scanning rate was 4 DEG/min, and the data sampling interval was 0.02 deg. By adopting the method, the negative electrode material respectively contains diffraction characteristic peaks (002), (100), (101), (102), (004) and (103) of graphite in the range of 2 theta belonging to 25.8-27.0 degrees, 41.7-42.9 degrees, 43.9-45.1 degrees, 49.5-51.5 degrees, 53.5-55.5 degrees and 58.7-60.7 degrees.
In the present invention, a laser particle size test method is employed for the median particle diameter Dv50 of the negative electrode material. For example, the measurement is carried out using a Malvern particle size tester, the test procedure is as follows: dispersing the negative electrode material in deionized water containing a dispersing agent (such as nonylphenol polyoxyethylene ether, the content of which is 0.03 wt%) to form a mixture, carrying out ultrasonic treatment on the mixture for 2min, and then placing the mixture into a Malvern particle size tester for testing.
In the present invention, the median diameter D isv50 means that 50% of the particles have a particle size smaller than this value in the volume-based particle size distribution.
In the present invention, the BET (Brunauer-Emmett-Teller) test method is used for the BET of the specific surface area of the negative electrode material. For example, the measurement was performed using Tri Star II specific surface Analyzer.
In the present invention, for the raman spectroscopy test, a Thermo Fisher raman spectrometer can be used for the test.
In the invention, an electron paramagnetic resonance method is adopted for the EPR resonance signal. For example, testing was performed using Bruker a200 electron paramagnetic resonance spectrometer.
In the invention, for the button type half cell test of the cathode material, a button type half cell manufacturing and testing method is adopted. For example, the following steps may be employed:
(1) mixing the negative electrode material, Super P, sodium carboxymethylcellulose and styrene butadiene rubber according to a mass ratio of 93.5: 1.0: 1.5: 4.0, adding deionized water, and uniformly mixing under the action of a vacuum stirrer to obtain negative electrode slurry;
(2) coating the negative electrode slurry obtained in the step (1) on a copper foil, drying in an oven at 80 ℃, and then transferring to a vacuum oven at 100 ℃ for drying for 12 hours to obtain the negative electrode slurry with the surface density of about 6.0mg/cm2The negative electrode sheet of (1);
(3) under a dry environment, the negative plate in the step (2) is arranged at a position of about 1.3g/cm3Compacting, rolling, and then preparing a negative electrode wafer with the diameter of 12mm by using a sheet punching machine;
(4) in a glove box, the negative electrode wafer in the step (3) is taken as a working electrode, a metal lithium sheet is taken as a counter electrode, a polyethylene diaphragm with the thickness of 20 mu m is taken as an isolating membrane, and electrolyte is added to assemble a button type half cell;
the electrolyte includes a solvent and a lithium salt; the solvent is one or more selected from Ethylene Carbonate (EC), Propylene Carbonate (PC), Propyl Propionate (PP), diethyl carbonate (DEC), fluoroethylene carbonate (FEC), 1, 3-Propanesultone (PS), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC); the lithium salt is selected from LiPF6、LiBF4、LiSbF6、LiClO4、LiCF3SO3、LiAlO4、LiAlCl4、Li(CF3SO2)2N, LiBOB and LiDFOB. For example, the electrolyte may be a mixture of an electrolyte with a mass ratio of EC: PC: PP: LiPF6: FEC: a mixed solution of PS 13:13:50:15:5: 4.
(5) Testing the button half cell in the step (4) by using a blue electricity (LAND) testing system, embedding lithium to 0.005V at a current of 0.1mA to obtain an embedded lithium capacity 1, standing for 10min, embedding lithium to 0.005V at a current of 0.05mA to obtain an embedded lithium capacity 2, standing for 10min, then removing lithium to 1.5V at a current of 0.1mA to obtain a first lithium removal capacity, wherein the sum of the embedded lithium capacity 1 and the embedded lithium capacity 2 is the first lithium insertion capacity, the gram capacity of the negative electrode material is obtained by dividing the first lithium removal capacity by the mass of the negative electrode material in the negative electrode wafer, and the first efficiency of the negative electrode material is obtained by dividing the first lithium removal capacity by the first lithium insertion capacity;
(6) cycling twice by the lithium intercalation and lithium deintercalation program in the step (5), taking the data of the second cycle to obtain the lithium intercalation and lithium deintercalation curves of the negative electrode material, and taking the capacity of the negative electrode material when the lithium is deintercalated to 0.3V as Q during the second lithium deintercalation1With the capacity of 1.5V for delithiation being Q2。
The invention also provides a negative electrode, which comprises a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode active material layer is arranged on at least one surface of the negative electrode current collector, and the negative electrode active material layer comprises the negative electrode material.
According to the present invention, the anode active material layer further includes a conductive agent. For example, the conductive agent is one or more selected from carbon black (Super P), acetylene black, Ketjen black, carbon fiber, single-walled carbon nanotubes (SWCNTs), and multi-walled carbon nanotubes.
According to the present invention, the anode active material layer further includes a binder. For example, the binder is one or more selected from carboxymethylcellulose, sodium carboxymethylcellulose, lithium carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyethylene, polyvinyl alcohol, polyvinyl chloride, polyvinyl fluoride, polyvinylpyrrolidone, polytetrafluoroethylene, polypropylene, Styrene Butadiene Rubber (SBR), and epoxy resin.
According to the present invention, the mass ratio of the anode material in the anode active material layer is 1% to 99%.
According to the invention, the negative current collector is one or more selected from copper foil, carbon-coated copper foil and perforated copper foil.
The invention also provides a lithium ion battery which comprises the negative electrode material and/or the negative electrode.
According to the invention, the lithium ion battery further comprises a positive plate.
According to the present invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on the surface of the positive electrode current collector. Preferably, the positive electrode active material layer includes a positive electrode material.
According to the invention, the positive current collector is selected from one or more of aluminum foil, carbon-coated aluminum foil and perforated aluminum foil.
According to the invention, the positive electrode material is selected from one or more of lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium iron silicate, Lithium Cobaltate (LCO), nickel cobalt manganese ternary material, nickel manganese/cobalt manganese/nickel cobalt binary material, lithium manganate and lithium-rich manganese-based material.
According to the present invention, the lithium ion battery further comprises a separator. For example, the membrane is selected from one or more of polyethylene membrane and polypropylene membrane.
According to the invention, the lithium ion battery further comprises an electrolyte. Preferably, the electrolyte is a nonaqueous electrolyte comprising a carbonate solvent and a lithium salt.
For example, the carbonate solvent is selected from one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), Propyl Propionate (PP), diethyl carbonate (DEC), fluoroethylene carbonate (FEC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC).
For example, the lithium salt is selected from LiPF6、LiBF4、LiSbF6、LiClO4、LiCF3SO3、LiAlO4、LiAlCl4、Li(CF3SO2)2N, LiBOB and LiDFOB.
According to the invention, the lithium ion battery further comprises an aluminum plastic film.
The invention has the beneficial effects that:
the amorphous carbon has the characteristics of interlayer lithium storage and pore lithium storage, and the amorphous carbon is used for coating the graphite, so that the gram volume of the graphite can be improved to a certain degree, the co-intercalation phenomenon of solvent molecules can be reduced, and the structural stability of the graphite is improved. However, the amorphous carbon has a large specific surface area and a large number of reaction sites, and when the amorphous carbon coating amount is more than 3%, side reactions in a high-temperature environment increase, and the deterioration of the battery capacity is accelerated. In order to improve the gram capacity of graphite and improve the high-temperature cycle capacity retention rate of the graphite, the invention provides a coating layer structure of a negative electrode material, wherein the property of a coating is between that of the graphite and amorphous carbon. In view of the above, the present application provides an anode material having at least one of the following characteristics:
(1) a high temperature carbonization product comprising graphite and an aromatic polymer on at least a portion of a surface of the graphite;
(2) the median diameter Dv50 is 6.0 to 20.0 μm, and the specific surface area BET is 0.5 to 6.5m2/g；
(3) Characteristic peak height I of Raman spectrum1And I2Satisfy 0.3 < I1/I2＜0.6；
(4) Having a resonance signal in an Electron Paramagnetic Resonance (EPR) test;
(5) in the button half cell test, delithiation was carried out toCapacity Q at 0.3V1And a capacity Q at delithiation to 1.5V2Satisfies 0.1 < (Q)2-Q1)/Q2＜0.4。
The cathode material has gram capacity higher than that of graphite, and when the cathode material is used as a cathode active material of a lithium ion battery, the lithium ion battery can have higher energy density and better high-temperature cycle capacity retention rate.
Specifically, the above feature (1) gives the main component of the anode material of the present invention.
Specifically, the above feature (2) shows the range of the median particle diameter and the specific surface area of the anode material of the present invention, and the anode material in this range has superior overall performance.
Specifically, the above feature (3) indicates that the carbon structure of the anode material of the present invention is ordered to a degree between that of graphite and amorphous carbon. I is1/I2The larger the ratio, the higher the degree of disorder of the carbon material. When the anode material of the invention is tested, I of the graphite material coated by the high-temperature carbonization product without the aromatic polymer is unexpectedly found1/I2The ratio is generally less than 0.2; and I of amorphous carbon material1/I2The ratio is generally greater than 1.0; and when the graphite is coated with amorphous carbon and the coating amount is more than 2%, I1/I2The ratio is generally greater than 0.7.
Specifically, the above feature (4) shows that the graphite surface in the negative electrode material of the present invention contains defect sites, and the defect sites contain unsaturated bonds, and the stable existence of the unsaturated bonds indicates that the graphite surface is protected by the coating, and also indicates that the coating and the graphite have strong interaction.
Specifically, the characteristic (5) shows that the negative electrode material of the invention has both the characteristics of lithium storage by graphite and lithium storage by amorphous carbon, and the two lithium storage capacities satisfy a certain proportional relationship, i.e., the mass ratio of the coating is 1-22%.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the anode material of example 3.
Fig. 2 is an X-ray diffraction (XRD) pattern of the negative electrode material of example 3.
Fig. 3 is a volume-based particle size distribution curve of the anode material of example 3.
Fig. 4 is a raman spectrum of the negative electrode material of example 3.
Fig. 5 is a graph of Electron Paramagnetic Resonance (EPR) signals for the anode material of example 3.
Fig. 6 is a lithium insertion and lithium removal curve for the negative electrode material of example 3.
Detailed Description
[ METHOD FOR PRODUCING NEGATIVE ELECTRODE MATERIAL ]
The invention also provides a method for preparing the anode material, which comprises the following steps:
(1) performing ball milling treatment on graphite in an inert atmosphere to obtain a first intermediate product;
(2) dissolving an aromatic polymer into a solvent, and uniformly mixing to obtain a first mixture;
(3) mixing the first intermediate product with the first mixture to obtain a second mixture;
(4) drying the second mixture to obtain a second intermediate product;
(5) carrying out high-temperature carbonization treatment on the second intermediate product in an inert atmosphere to obtain a third intermediate product;
(6) and grinding the third intermediate product to obtain the cathode material.
According to the invention, in the step (1), the ball milling comprises planetary ball milling, horizontal ball milling, vibration ball milling and the like.
According to the invention, in the step (1), the median particle diameter Dv50 of the first intermediate product is 6.0-12.0 μm, and the specific surface area BET is 10.0-50.0 m2/g。
According to the invention, in step (2), the aromatic polymer is as defined above.
According to the invention, in step (2), the mass ratio y of the aromatic polymer to the first intermediate product satisfies 0.05. ltoreq. y.ltoreq.1.4, illustratively 0.05, 0.1, 0.2, 0.5, 0.8, 1.0, 1.2, 1.4 or any point within the range of values of the aforementioned two.
According to the present invention, in the step (2), the solvent is an organic solvent. Illustratively, the organic solvent is selected from one or more of toluene, xylene, chlorobenzene and aniline.
According to the invention, in the step (5), the high-temperature carbonization treatment step is as follows: heating to 200-300 ℃ at a heating rate of 1-4 ℃/min, and keeping for 1-3 h; and then heating to 600-800 ℃ at the heating rate of 1-4 ℃/min, and keeping for 2-5 h.
According to research, the aromatic polymer presents a flaky shape after high-temperature carbonization treatment. X-ray diffraction analysis revealed that these flakes were crystalline to a degree between amorphous carbon and graphite. The BET test found that these flakes had a specific surface area of about 10m2G, less than amorphous carbon (> 50 m)2/g), which is presumed to have a lower micropore density than amorphous carbon. Meanwhile, the invention also utilizes a mechanical crushing method to manufacture a small amount of defect sites on the surface of the graphite, so that unsaturated bonds are generated to form strong interaction with conjugated pi bonds of the aromatic polymer, and a graphite-cladding layer interface structure with high stability can be obtained. On the basis of this, by increasing the amount of the surface aromatic polymer to be coated, a negative electrode material having excellent performance can be obtained.
The invention also provides a preparation method of the cathode, which comprises the following steps:
and mixing the negative electrode material, an optional conductive agent and a binder to obtain negative electrode slurry, coating the negative electrode slurry on a current collector, drying, slicing, drying, and finally rolling and slitting to obtain the negative electrode sheet.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Examples 1 to 6
The preparation method, parameters and physicochemical properties of the anode material are given below by way of example.
The following steps are adopted in examples 1-6 to prepare the negative electrode material:
(1) performing ball milling treatment on graphite in an inert atmosphere to obtain a first intermediate product;
the graphite was an uncoated artificial graphite, commercially available, having a Dv50 of about 17.0 μm and a BET of about 1.2m2In terms of volume, the first intermediate product has a Dv50 of about 7.6. mu.m, a BET of about 33.1m2/g。
(2) Dissolving polynaphthalene with the number average molecular weight of 2000 into toluene, and uniformly mixing to obtain a first mixture;
(3) pouring the first intermediate product into the first mixture, and fully stirring to obtain a second mixture;
(4) drying the second mixture to obtain a second intermediate product;
(5) putting the second intermediate product into a high-temperature furnace, heating to 250 ℃ at a heating rate of 3 ℃/min, and keeping for 3 hours; then heating to 600 ℃ at the heating rate of 3 ℃/min, and keeping for 3h to obtain a third intermediate product;
(6) and grinding the third intermediate product to obtain the cathode material.
TABLE 1-1
Table 1-1 shows the mass ratio y of polynaphthalene to the first intermediate product in step (3) in examples 1 to 6. Table 1-1 also shows the physical and chemical properties (including median diameter Dv50, specific surface area BET, and Raman spectrum I) of the negative electrode materials of examples 1-61/I2Ratio, presence or absence of EPR resonance signal, gram capacity, first effect, capacity ratio (Q)2-Q1)/Q2)。
As can be seen from Table 1-1, the median particle diameters Dv50 of the negative electrode materials of examples 1 to 6 were successively larger and were all in the range of 6.0 to 20.0. mu.m.
As can be seen from Table 1-1, the BET of the negative electrode materials of examples 1 to 6 is 0.5 to 6.5m2In the range of/g.
As can be seen from Table 1-1, as the mass ratio y of the aromatic polymer to the first intermediate product increases, I of the negative electrode materials obtained in examples 1 to 6 increases1/I2The ratio increases in turn, indicating an increase in the overall degree of disorder of the carbon structure.
As can be seen from Table 1-1, the negative electrode materials of examples 1 to 6 all have EPR resonance signals, which indicates that the negative electrode materials prepared in examples 1 to 6 all contain unpaired electrons, and the coating and graphite have strong bonding effect.
As can be seen from the table 1-1, the gram capacities of the negative electrode materials of the embodiments 1 to 6 are sequentially increased, and the gram capacities of the negative electrode materials of the embodiments 2 to 6 are all more than or equal to 355 mAh/g; the first effect of the negative electrode materials of the embodiments 1 to 6 is increased and then reduced, and the first effect is more than 89%.
As can be seen from Table 1-1, the capacity ratios (Q) of the negative electrode materials of examples 1 to 62-Q1)/Q2The increase in the sizes indicated that the disordered carbon content of the negative electrode materials of examples 1 to 6 was gradually increased. Except for capacity ratio (Q) of example 12-Q1)/Q2The content of the compound is not less than 0.082, and the other embodiments are all in the range of 0.1-0.4.
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the anode material of example 3. As can be seen from the figure, after the ball milling treatment is performed on the artificial graphite in example 3, the prepared negative electrode material still retains the sheet-like morphology characteristics similar to those of the artificial graphite, so that the structural stability of the negative electrode material can be ensured.
Fig. 2 is an X-ray diffraction (XRD) pattern of the negative electrode material of example 3. As can be seen from the figure, the negative electrode material exhibits the crystal diffraction characteristics of graphite, indicating that it retains the basic structure of artificial graphite, and thus can secure the structural stability of the negative electrode material.
Fig. 3 is a volume-based particle size distribution curve of the anode material of example 3. As can be seen, the Dv50 of the negative electrode material is about 12.6 μm, which is greater than Dv50(7.6 μm) of the first intermediate product, indicating that the carbonization of the aromatic polymer at high temperature re-aggregates the fine particles, thus reducing the specific surface area of the negative electrode material and further reducing the side reactions at high temperature.
Fig. 4 is a raman spectrum of the negative electrode material of example 3. As can be seen from the figure, I of the anode material1/I2The ratio was about 0.40, which is greater than I of the artificial graphite in comparative example 11/I2The ratio (0.16) was smaller than that of the negative electrode material (0.72) coated with amorphous carbon in comparative example 2. This indicates that: example 3 the carbon structure of the coating has an order between that of graphite and amorphous carbon, which has a higher lithium insertion capacity than graphite and a higher cycling stability than amorphous carbon.
Fig. 5 is a graph of Electron Paramagnetic Resonance (EPR) signals for the anode material of example 3. As can be seen from the figure, the cathode material has EPR resonance signals, which indicate that unpaired electrons exist on the surface of graphite, and the unpaired electrons are generated after the graphite is ball-milled and stably exist after the aromatic polymer is carbonized and coated at high temperature, so that the anode material can form a chemical bonding effect with conjugated large pi bonds of benzene rings to improve the structural stability of a coating.
Fig. 6 is a lithium insertion and lithium removal curve for the negative electrode material of example 3. As can be seen from the figure, the lithium removal capacity of the negative electrode material above 0.3V accounts for 19.6% of the total lithium removal capacity, and the part of the capacity is mainly from the coating. Further, the coating of the invention contains abundant micropores which can contain lithium ions, so that the theoretical gram capacity of lithium storage of the coating is higher than that of an ordered layered structure, and the gram capacity of the negative electrode material is higher than that of graphite and reaches about 381 mAh/g.
Comparative examples 1 to 4
The negative electrode material of comparative example 1 was an uncoated artificial graphite, commercially available, having a Dv50 of about 17.0 μm and a BET of about 1.2m2/g。
Comparative examples 2 to 4 the following steps were used to prepare the negative electrode materials:
(1) putting graphite into a vapor deposition device, and introducing argon for protection;
the graphite is an uncoated synthetic graphite, commercially available, having a Dv50 of about 17.0 μm and a BET of about 1.2m2/g；
(2) Heating to 700 deg.C at 10 deg.C/min;
(3) changing the introduced gas to C2H2Argon/acetylene mixed gas with the content of 10 percent, and the reaction time is t (see table 2-1);
(4) and replacing the introduced gas with argon, and naturally cooling to room temperature to obtain the cathode material.
Table 2-1 shows the reaction time t in step (3) for comparative examples 2 to 4. Table 2-1 also shows the physical and chemical properties (including median diameter Dv50, specific surface area BET, and Raman spectrum I) of the negative electrode materials of comparative examples 2-41/I2Ratio, presence or absence of EPR resonance signal, gram capacity, first effect, capacity ratio (Q)2-Q1)/Q2)。
TABLE 2-1
Note: in the table, "\" indicates that t ═ 0.
As can be seen from Table 2-1, the Dv50 of the negative electrode materials of comparative examples 1 to 4 increased in order and were all in the range of 6.0 to 20.0. mu.m.
As can be seen from Table 2-1, the BET of the negative electrode materials of comparative examples 1 to 4 increases in order, and are all 0.5 to 6.5m2In the range of/g.
As can be seen from Table 2-1, I of the anode material of comparative example 11/I2Ratio less than 0.2, and I of the negative electrode materials of comparative examples 2 to 41/I2The ratios are sequentially increased and are all larger than 0.7, which shows that the graphite material coated with amorphous carbon is formed in the anode materials of comparative examples 2-4.
As can be seen from Table 2-1, the negative electrode materials of comparative examples 1 to 4 have no EPR resonance signal, which indicates that the negative electrode material coatings of comparative examples 1 to 4 do not have strong bonding effect with graphite.
As can be seen from Table 2-1, the gram capacities of the negative electrode materials of comparative examples 1 to 4 are sequentially increased, and first effect is increased and then reduced.
As can be seen from Table 2-1, the capacity ratios (Q) of the negative electrode materials of comparative examples 1 to 42-Q1)/Q2And increases in turn.
Comparative examples 5 to 9
The negative electrode materials of comparative examples 5 to 9 were obtained by mixing graphite and hard carbon, and the ratio of the mass of graphite divided by the mass of hard carbon was z.
The graphite was an uncoated artificial graphite commercially available as Dv50 of about 17.0 μm and BET of about 1.2m2/g。
The hard carbon is obtained from commercial purchase and has the following characteristics: dv50 was about 13.0. mu.m, BET was about 2.4m2The volume of 0.005-1.5V g is about 402mAh/g, and the first effect is about 71.6%.
Table 3-1 shows the ratio z of the mass of graphite divided by the mass of hard carbon in comparative examples 5 to 9 (z increases in turn in comparative examples 5 to 9, and the blending of hard carbon increases in turn). Table 3-1 also shows the physical and chemical properties (including median diameter Dv50, specific surface area BET, and Raman spectrum I) of the negative electrode materials of comparative examples 5 to 91/I2Ratio, presence or absence of EPR resonance signal, gram capacity, first effect, capacity ratio (Q)2-Q1)/Q2)。
TABLE 3-1
As can be seen from Table 3-1, the Dv50 of the negative electrode materials of comparative examples 5 to 9 decreased in order and were all in the range of 6.0 to 20.0. mu.m.
As can be seen from Table 3-1, the BET values of the negative electrode materials of comparative examples 5 to 9 are sequentially increased and are all 0.5 to 6.5m2In the range of/g.
As can be seen from Table 3-1, I of the negative electrode materials of comparative examples 5 to 91/I2The ratio increases in turn.
As can be seen from Table 3-1, the negative electrode materials of comparative examples 5 to 9 all had no EPR resonance signal.
As can be seen from Table 3-1, the gram capacities of the negative electrode materials of comparative examples 5 to 9 were sequentially increased, and the first effects were sequentially decreased.
As can be seen from Table 3-1, the capacity ratio (Q) of the negative electrode materials of comparative examples 5 to 92-Q1)/Q2And increases in turn.
Examples 7 to 12 and comparative examples 10 to 18
Lithium ion batteries were prepared using the negative electrode materials of examples 1 to 6 and comparative examples 1 to 9, respectively.
The manufacturing method of the lithium ion battery comprises the following steps:
(1) respectively mixing the negative electrode materials of examples 1-6 and comparative examples 1-9, sodium carboxymethyl cellulose, styrene butadiene rubber and Super P according to the mass ratio of 96.5:1.6:1.6:0.3, adding deionized water, and obtaining negative electrode slurry under the action of a vacuum stirrer. Uniformly coating the negative electrode slurry on a copper foil with the thickness of 8 mu m, wherein the surface density of the negative electrode slurry coated on the surface of the negative electrode current collector is 11.0mg/cm2. And transferring the copper foil to an oven at 80 ℃ for drying for 12h, and then rolling and slitting to obtain the negative plate.
(2) Mixing Lithium Cobaltate (LCO), polyvinylidene fluoride (PVDF), acetylene black and Carbon Nanotubes (CNTs) according to the mass ratio of 96:2:1.5:0.5, adding N-methyl pyrrolidone, and stirring under the action of a vacuum stirrer until uniform anode slurry is mixed. And uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 12 mu m, baking the coated aluminum foil in an oven, then transferring the aluminum foil into the oven with the temperature of 120 ℃ for drying for 8h, and then rolling and cutting to obtain the required positive electrode plate. (the size of the positive plate is smaller than that of the negative plate, and the reversible capacity of the positive plate per unit area is 4 percent lower than that of the negative plate.)
(3) Under an inert atmosphere, the mass ratio of the components is 15: 15: to a 50 Ethylene Carbonate (EC), Propylene Carbonate (PC) and Propyl Propionate (PP) mixed solution was rapidly added 14 wt% of well-dried lithium hexafluorophosphate (LiPF)6) And 6 wt% fluoroethylene carbonate (FEC), stirring well, passing throughAfter the moisture and the free acid are detected to be qualified, the required electrolyte is obtained;
selecting a polyethylene diaphragm with the thickness of 8 mu m;
the prepared positive plate, the diaphragm and the prepared negative plate are stacked in sequence, the diaphragm is positioned between the positive plate and the negative plate to play a role in isolation, and then the naked battery cell is obtained through winding. Placing the bare cell in an aluminum-plastic film shell, injecting electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping, sorting and other processes to obtain the required lithium ion battery.
The test method of the lithium ion battery comprises the following steps:
(1) a blue electron (LAND) test system was used, with a test temperature of 45 ℃.
(2) Charging to 4.45V at constant current of 0.7C, charging to 0.05C at constant voltage, standing for 10min, discharging to 3.0V at 0.2C to obtain discharge capacity and discharge energy, wherein the discharge capacity is taken as the nominal capacity, and the discharge energy is divided by the volume of the battery to be taken as the energy density of the battery.
(3) The thickness of the battery at this time was measured by constant current charging to 3.85V at 0.7C and constant voltage charging to 0.01C, and this was taken as the initial thickness of the battery.
(4) Charging to 4.45V at constant current of 1.5C, charging to 0.05C at constant voltage, standing for 10min, discharging to 3.0V at 1C, standing for 10min, cycling through the charging and discharging steps, taking the highest value of the discharging capacity in the previous three weeks as the initial capacity of the battery, taking the ratio of the capacity in each step to the initial capacity as the capacity conservation rate of the battery, and cycling to 800 th week. The thickness of the battery is tested every 100 weeks, and the difference between the thickness and the initial thickness is divided by the initial thickness to obtain the thickness expansion rate of the battery.
The performance test results and descriptions of the lithium ion batteries are as follows:
table 4-1 shows the test performance results (including nominal capacity, energy density, capacity retention at 800 cycles, and thickness expansion at 800 cycles) of the lithium ion batteries of examples 7 to 12, which were manufactured based on the negative electrode materials of examples 1 to 6, and the lithium ion batteries of comparative examples 10 to 18, which were manufactured based on the negative electrode materials of comparative examples 1 to 9.
TABLE 4-1
As can be seen from Table 4-1, the nominal capacity of the lithium ion batteries of examples 7 to 12 is in the range of 3700 to 3770mAh, the nominal capacity of the lithium ion batteries of comparative examples 10 to 13 is in the range of 3730 to 3750mAh, and the nominal capacity of the lithium ion batteries of comparative examples 14 to 18 is in the range of 3670 to 3740 mAh.
As can be seen from Table 4-1: the energy density of the lithium ion batteries of the embodiments 7 to 12 is sequentially improved, and the range is 730 to 760 Wh/L; the energy density of the lithium ion batteries of the comparative examples 10 to 13 is 730 to 740 Wh/L; the energy density of the lithium ion batteries of comparative examples 14 to 18 was reduced in sequence, ranging from 680 to 740 Wh/L. The comparison shows that the gram capacity of the negative electrode materials of the examples 2 to 6 is higher than that of the comparative example 1, and correspondingly, the lithium ion batteries of the examples 8 to 12 have energy density similar to or higher than that of the lithium ion battery of the comparative example 10.
As can be seen from Table 4-1: the capacity retention rate of the lithium ion batteries of examples 7 to 12 is within the range of 82.0 to 83.0%, and the thickness expansion rates are all less than 10.1%; the capacity retention rates of the lithium ion batteries of the comparative examples 10 to 13 are all less than 76%, and the thickness expansion rate is within the range of 10.7 to 11.0%; the capacity retention rates of the lithium ion batteries of comparative examples 14 to 18 are all less than 74%, and the thickness expansion rates are all greater than 11.0%. As can be seen by comparison, the lithium ion batteries of examples 7 to 12 have higher capacity retention rate and lower thickness expansion rate.
From the above results, it can be seen that the gram capacity of the negative electrode materials of embodiments 2 to 6 of the present invention is higher than that of graphite, and the lithium ion battery prepared based on the negative electrode materials has a higher energy density and shows a better capacity retention rate in a high temperature cycle. The surfaces of the graphite in the negative electrode materials of comparative examples 2-4 are coated by amorphous carbon, and the negative electrode materials of comparative examples 5-9 are physical mixture of graphite and hard carbon, so that the prepared lithium ion batteries of comparative examples 11-13 and 14-18 cannot simultaneously ensure that the negative electrode materials have high gram capacity and high capacity retention rate in high-temperature cycle.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An anode material, comprising graphite and a coating on at least a portion of a surface of the graphite; the anode material has at least one of the following characteristics:
1) in the Raman spectrum test, the Raman shift is 1300-1400cm-1、1550-1650cm-1The region has a height of I1、I2Characteristic peak of (1), and 0.3 < I1/I2＜0.6；
2) The negative electrode material has a resonance signal in an Electron Paramagnetic Resonance (EPR) test.
2. The negative electrode material of claim 1, wherein the coating is a high temperature carbonization product of an aromatic polymer.
3. The negative electrode material of claim 2, wherein the coating has a degree of crystallinity between that of graphite and amorphous carbon;
and/or, the aromatic polymer is selected from homopolymers or copolymers of aromatic ring compounds; the aromatic ring compound is selected from at least one of naphthalene, biphenyl, anthracene, phenanthrene, perylene and pyrene.
4. The anode material according to claim 3, wherein a specific surface area of the clad is lower than that of amorphous carbon.
5. The negative electrode material of claim 1, wherein the coating is present in an amount of 1 to 22% by mass.
6. The negative electrode material according to claim 1, wherein the negative electrode material has a median particle diameter Dv50 of 5.0 μm to 20.0 μm;
and/or the specific surface area BET of the negative electrode material is 0.5-6.5 m2/g。
7. The negative electrode material of any one of claims 1 to 6, wherein the negative electrode material has a capacity Q at delithiation to 0.3V in a button half cell test1With the capacity of 1.5V for delithiation being Q2Then Q is1And Q2Satisfies 0.1 < (Q)2-Q1)/Q2＜0.4。
8. An anode, characterized in that the anode comprises an anode current collector and an anode active material layer, the anode active material layer is provided on at least one surface of the anode current collector, and the anode active material layer comprises the anode material according to any one of claims 1 to 7.
9. The negative electrode according to claim 8, wherein the negative electrode material is contained in the negative electrode active material layer in an amount of 1% to 99% by mass.
10. A lithium ion battery comprising the negative electrode material according to any one of claims 1 to 7, or comprising the negative electrode according to claim 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210126300.9A CN114551829A (en) | 2022-02-10 | 2022-02-10 | Cathode material and lithium ion battery containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210126300.9A CN114551829A (en) | 2022-02-10 | 2022-02-10 | Cathode material and lithium ion battery containing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114551829A true CN114551829A (en) | 2022-05-27 |
Family
ID=81673974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210126300.9A Pending CN114551829A (en) | 2022-02-10 | 2022-02-10 | Cathode material and lithium ion battery containing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114551829A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006066334A (en) * | 2004-08-30 | 2006-03-09 | Japan Energy Corp | Carbon material and nonaqueous electrolyte solution secondary cell using above |
| JP2011216231A (en) * | 2010-03-31 | 2011-10-27 | Jx Nippon Oil & Energy Corp | Carbon material for lithium ion secondary battery, and electrode using the same |
| JP2013008526A (en) * | 2011-06-23 | 2013-01-10 | Hitachi Chem Co Ltd | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN103190018A (en) * | 2010-09-24 | 2013-07-03 | 日立化成株式会社 | Lithium ion battery, and battery module utilizing same |
| JP2014216125A (en) * | 2013-04-24 | 2014-11-17 | 日本電気株式会社 | Graphite-based electrode active material, electrode and storage battery |
| CN104247107A (en) * | 2012-04-19 | 2014-12-24 | 株式会社日立制作所 | Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| JP2016219275A (en) * | 2015-05-21 | 2016-12-22 | 日立マクセル株式会社 | Lithium ion secondary battery |
| US20180248187A1 (en) * | 2015-09-09 | 2018-08-30 | Nec Corporation | Fast chargeable carbon anode material with inner channels |
| CN110915033A (en) * | 2017-12-01 | 2020-03-24 | 株式会社Lg化学 | Negative electrode for lithium secondary battery and lithium secondary battery including the same |
| CN111164804A (en) * | 2019-12-30 | 2020-05-15 | 上海杉杉科技有限公司 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| WO2021192650A1 (en) * | 2020-03-24 | 2021-09-30 | 東海カーボン株式会社 | Negative electrode material for lithium ion secondary batteries, method for producing negative electrode material for lithium ion secondary batteries, and material for producing negative electrode material for lithium ion secondary batteries |
| CN113594436A (en) * | 2021-07-22 | 2021-11-02 | 珠海冠宇电池股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery comprising negative electrode material |
-
2022
- 2022-02-10 CN CN202210126300.9A patent/CN114551829A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006066334A (en) * | 2004-08-30 | 2006-03-09 | Japan Energy Corp | Carbon material and nonaqueous electrolyte solution secondary cell using above |
| JP2011216231A (en) * | 2010-03-31 | 2011-10-27 | Jx Nippon Oil & Energy Corp | Carbon material for lithium ion secondary battery, and electrode using the same |
| CN103190018A (en) * | 2010-09-24 | 2013-07-03 | 日立化成株式会社 | Lithium ion battery, and battery module utilizing same |
| JP2013008526A (en) * | 2011-06-23 | 2013-01-10 | Hitachi Chem Co Ltd | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN104247107A (en) * | 2012-04-19 | 2014-12-24 | 株式会社日立制作所 | Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| JP2014216125A (en) * | 2013-04-24 | 2014-11-17 | 日本電気株式会社 | Graphite-based electrode active material, electrode and storage battery |
| JP2016219275A (en) * | 2015-05-21 | 2016-12-22 | 日立マクセル株式会社 | Lithium ion secondary battery |
| US20180248187A1 (en) * | 2015-09-09 | 2018-08-30 | Nec Corporation | Fast chargeable carbon anode material with inner channels |
| CN110915033A (en) * | 2017-12-01 | 2020-03-24 | 株式会社Lg化学 | Negative electrode for lithium secondary battery and lithium secondary battery including the same |
| CN111164804A (en) * | 2019-12-30 | 2020-05-15 | 上海杉杉科技有限公司 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| WO2021192650A1 (en) * | 2020-03-24 | 2021-09-30 | 東海カーボン株式会社 | Negative electrode material for lithium ion secondary batteries, method for producing negative electrode material for lithium ion secondary batteries, and material for producing negative electrode material for lithium ion secondary batteries |
| CN113594436A (en) * | 2021-07-22 | 2021-11-02 | 珠海冠宇电池股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery comprising negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| BUILDING A CYCLE-STABLE FE–SI ALLOY/CARBON NANOCOMPOSITE ANODE FOR LI-ION BATTERIES THROUGH A COVALENT-BONDING METHOD: "Building a Cycle-Stable Fe–Si Alloy/Carbon Nanocomposite Anode for Li-Ion Batteries through a Covalent-Bonding Method", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 12, pages 30503 - 30509 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021108983A1 (en) | Secondary battery, device, artificial graphite, and preparation method therefor | |
| WO2021108982A1 (en) | Artificial graphite, secondary battery, preparation method, and device | |
| CN113207313B (en) | Secondary battery, device, artificial graphite and preparation method | |
| US11901557B2 (en) | Negative electrode active material, method for preparing same, secondary battery and apparatus including the secondary battery | |
| CN114864909A (en) | Negative electrode material, negative plate comprising negative electrode material and battery | |
| US20230369591A1 (en) | Negative-electrode active material and preparation method thereof, secondary battery, and battery module, battery pack, and apparatus containing such secondary battery | |
| CN113594436A (en) | Negative electrode material, preparation method thereof and lithium ion battery comprising negative electrode material | |
| CN116053434A (en) | Negative electrode material, secondary battery and electronic device | |
| KR102519438B1 (en) | Composite anode active material, lithium battery comprising the same, and method of preparing the composite anode active material | |
| CN114982009B (en) | Negative electrode material, negative electrode sheet, electrochemical device and electronic device comprising same | |
| CN114464804A (en) | Cathode material and lithium ion battery containing same | |
| CN116895760A (en) | Negative electrode active material, negative electrode sheet, lithium ion battery and electronic device | |
| US20230146274A1 (en) | Silicon carbon negative electrode material, negative electrode sheet, secondary battery, battery module, battery pack and power consumption apparatus | |
| US11569498B2 (en) | Negative electrode active material and method for preparation thereof, secondary battery, and apparatus including secondary battery | |
| CN115832232B (en) | Negative electrode active material, negative electrode sheet, secondary battery, battery module, battery pack, and power device | |
| CN112310357A (en) | Silicon-oxygen compound and secondary battery containing same | |
| CN114142015A (en) | Negative electrode material and battery comprising same | |
| CN114551829A (en) | Cathode material and lithium ion battery containing same | |
| EP4207372A1 (en) | Secondary battery and electric device | |
| CN114497489A (en) | Composite material, negative plate and battery comprising same | |
| CN116632154A (en) | Negative plate and lithium ion battery comprising same | |
| CN117038881A (en) | Composite phosphate positive electrode material, preparation method thereof, positive electrode plate and secondary battery | |
| CN116632225A (en) | Long-cycle negative plate and lithium ion battery comprising same | |
| CN116632155A (en) | Super fast-charging negative plate and lithium ion battery comprising same | |
| CN115810741A (en) | Negative active material, method of preparing the same, and secondary battery and device using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |