CN117117185A - Lithium-rich composite material and preparation method and application thereof - Google Patents
Lithium-rich composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117117185A CN117117185A CN202310961106.7A CN202310961106A CN117117185A CN 117117185 A CN117117185 A CN 117117185A CN 202310961106 A CN202310961106 A CN 202310961106A CN 117117185 A CN117117185 A CN 117117185A
- Authority
- CN
- China
- Prior art keywords
- lithium
- rich
- aluminum
- containing compound
- layer
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 340
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 339
- 239000002131 composite material Substances 0.000 title claims abstract description 174
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 372
- 150000001875 compounds Chemical class 0.000 claims abstract description 119
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 97
- 239000010936 titanium Substances 0.000 claims abstract description 67
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 59
- -1 aluminum compound Chemical class 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 222
- 238000001354 calcination Methods 0.000 claims description 66
- 239000002245 particle Substances 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000003513 alkali Substances 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 230000008859 change Effects 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 18
- 238000004729 solvothermal method Methods 0.000 claims description 14
- 239000002344 surface layer Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 239000002352 surface water Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000006104 solid solution Substances 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims description 5
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000008707 rearrangement Effects 0.000 abstract description 11
- 230000008093 supporting effect Effects 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 150000003609 titanium compounds Chemical class 0.000 abstract description 5
- 239000007774 positive electrode material Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 31
- 229910001416 lithium ion Inorganic materials 0.000 description 29
- 230000000670 limiting effect Effects 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 230000002829 reductive effect Effects 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 229910010093 LiAlO Inorganic materials 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 14
- 230000001502 supplementing effect Effects 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 238000005538 encapsulation Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 239000011883 electrode binding agent Substances 0.000 description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 4
- 239000011532 electronic conductor Substances 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910018553 Ni—O Inorganic materials 0.000 description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- QRVIVVYHHBRVQU-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QRVIVVYHHBRVQU-UHFFFAOYSA-H 0.000 description 3
- 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 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000010406 interfacial reaction Methods 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000005287 vanadyl group Chemical group 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- 229940118662 aluminum carbonate Drugs 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 125000003184 C60 fullerene group Chemical group 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 1
- 229910020719 Li0.33 La0.56 Inorganic materials 0.000 description 1
- 229910003055 Li0.33 La0.57 TiO3 Inorganic materials 0.000 description 1
- 229910021102 Li0.5La0.5TiO3 Inorganic materials 0.000 description 1
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- 229910006406 SnO 2 At Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical class [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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Abstract
The application provides a lithium-rich composite material, a preparation method and application thereof, wherein the lithium-rich composite material comprises a first functional material and a lithium-rich material layer, and at least part of the first functional material is distributed in the lithium-rich material layer; the first functional material comprises at least one of a first aluminum-containing compound and a first titanium-containing compound. According to the lithium-rich composite material, the first functional material contains at least one of the aluminum compound or the titanium compound, is distributed in the lithium-rich material layer, can play a supporting role of a framework, inhibits rearrangement of lithium and other non-oxygen elements in the lithium-rich material to a certain extent, and effectively improves the cycle performance of the lithium-rich composite material.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a lithium-rich composite material and a preparation method and application thereof.
Background
In recent years, there has been an urgent need to improve the efficiency of energy storage and extraction to meet the urgent demands for long standby of portable electronic devices and high energy density, long cycle of electric vehicles. In general, in a lithium ion battery, a negative electrode is called an SEI film in a first charge and discharge process to consume part of active lithium, thereby resulting in a reduction in the capacity of the battery. The addition of a sacrificial lithium source additive of high theoretical specific capacity to the positive electrode of a battery is one of the most promising strategies to reduce the initial capacity loss of the negative electrode.
However, the inventor finds that the existing sacrificial lithium source additive also has the problems of unstable internal structure, easy rearrangement of lithium and other non-oxygen elements, high residual alkali, easy deterioration in air, low lithium utilization rate, and the like, and the cycle and rate performance of the existing sacrificial lithium source additive are still to be improved.
Therefore, there is a need to develop a lithium-rich composite material that has at least one of the following advantages, so that it can be used at least as a lithium-supplementing material to improve the electrochemical performance of a lithium ion battery:
(1) The internal structure is stable, and the rearrangement of lithium and other non-oxygen elements can be inhibited, so that the cycle performance is improved;
(2) Can reduce residual alkali, has high stability in air, high lithium utilization rate and good rate capability.
Disclosure of Invention
In view of the above, an object of the present application is to provide a lithium-rich composite material, in which the first functional material contains at least one of an aluminum compound or a titanium compound, and is distributed inside the lithium-rich material layer, so as to play a role in supporting a skeleton, inhibit rearrangement of lithium and other non-oxygen elements in the lithium-rich material to a certain extent, and effectively improve the cycle performance of the lithium-rich composite material.
The application further aims at providing a preparation method of the lithium-rich composite material.
It is yet another object of the present application to provide a positive electrode.
It is still another object of the present application to provide a secondary battery.
In order to achieve the above objective, an embodiment of a first aspect of the present application provides a lithium-rich composite material, which includes a first functional material and a lithium-rich material layer, at least a portion of the first functional material is distributed inside the lithium-rich material layer; the first functional material comprises at least one of a first aluminum-containing compound and a first titanium-containing compound.
In some embodiments, the first functional material and the lithium-rich material in the lithium-rich material layer form a solid solution having a chemical formula of Li a Q 1-m R m O n Wherein, the method comprises the steps of, wherein,q comprises at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn, R comprises at least one of Al and Ti, a is more than or equal to 2 and less than or equal to 8, m is more than or equal to 0 and less than or equal to 0.2, and n is more than 0 and less than 7.
In some embodiments, the lithium-rich composite comprises a core, an intermediate layer, and an outer layer disposed in that order, the core comprising at least a portion of the first functional material, the intermediate layer comprising the layer of lithium-rich material; the outer layer includes a second functional material including at least one of a second aluminum-containing compound, a second titanium-containing compound.
In some embodiments, the intermediate layer is coated on the outer surface of the inner core continuously or discontinuously.
In some embodiments, the outer layer is coated on the outer surface of the middle layer continuously or discontinuously.
In some embodiments, the particle size of the first functional material is less than or equal to the particle size of the second functional material.
In some embodiments, the first aluminum-containing compound and the second aluminum-containing compound each comprise at least one of an aluminum lithium compound, an inorganic aluminum compound.
In some embodiments, the first titanium-containing compound and the second titanium-containing compound each comprise a titanium lithium compound.
In some embodiments, the mass ratio of the inner core, the intermediate layer, and the outer layer is (0.1-10): 100 (0.1-10).
In some embodiments, the first aluminum-containing compound or/and the first titanium-containing compound is present in the lithium-rich composite in an amount of 0.1 to 10wt%.
In some embodiments, the second aluminum-containing compound or/and the second titanium-containing compound is present in the lithium-rich composite in an amount of 0.1 to 10wt%.
In some embodiments, when the first functional material contains the first aluminum-containing compound and the second functional material contains the second aluminum-containing compound, the mass ratio of aluminum element in the first functional material to aluminum element in the second functional material is (0.2-1): 1.
In some embodiments, the lithium-rich material in the lithium-rich material layer includes a material having the formula Li x M y O z Is a material of (2); wherein M comprises at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn, x is more than or equal to 2 and less than or equal to 8, y is more than or equal to 0 and less than or equal to 5, and z is more than 0 and less than 7.
In some embodiments, the particle size of the lithium-rich composite ranges from 0.5 to 25.0 μm.
In some embodiments, the lithium-rich composite has a residual alkali content of less than 1500ppm.
In some embodiments, the surface moisture content of the lithium-rich composite is less than 300ppm.
In some embodiments, the lithium-rich composite has a rate of change of volume during charge and discharge of less than 10%.
In order to achieve the above object, a second aspect of the present application provides a method for preparing a lithium-rich composite material, comprising:
uniformly mixing a lithium source, an M source and at least part of metal sources of a first functional material, and then sequentially carrying out first calcination and second calcination to obtain a lithium-rich material layer material containing the first functional material inside;
the M element in the M source includes at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn.
In some embodiments, the method of preparing a lithium-rich composite further comprises:
After dissolving a second functional material metal source, uniformly mixing the dissolved second functional material metal source with the material of the lithium-rich material layer containing the first functional material inside to obtain a mixed suspension;
and sequentially carrying out solvothermal reaction and third calcination on the mixed suspension to obtain the lithium-rich composite material.
To achieve the above objective, an embodiment of a third aspect of the present application provides a positive electrode, which includes the lithium-rich composite material according to the embodiment of the present application or the lithium-rich composite material prepared by the method for preparing the lithium-rich composite material according to the embodiment of the present application.
In order to achieve the above object, a fourth aspect of the present application provides a secondary battery including a positive electrode, a negative electrode, and a separator, the positive electrode being the positive electrode of the embodiment of the present application.
The lithium-rich composite material provided by the embodiment of the application has at least the following beneficial effects:
1. the first functional material contains at least one of an aluminum compound or a titanium compound, is distributed inside the lithium-rich material layer, can play a supporting role of a framework, inhibits rearrangement of lithium and other non-oxygen elements in the lithium-rich material to a certain extent, and effectively improves the cycle performance of the lithium-rich composite material.
2. When the lithium-rich composite material further comprises an outer layer, the inner core containing the first functional material, the middle layer containing the lithium-rich material layer and the outer layer containing the second functional material form a cage-shaped structure, wherein the first functional material of the inner core plays a role in supporting a framework, the rearrangement of lithium and other non-oxygen elements in the lithium-rich material is inhibited to a certain extent, the cycle performance of the lithium-rich material is effectively improved, and the second functional material of the outer layer can reduce the surface residual alkali content of the lithium-rich composite material. In addition, the volume change rate of the whole lithium-rich composite material in the charge and discharge process is low, the electrode/electrolyte reaction is reduced, the conductivity of the material is improved, the defect of the lithium-rich material is increased, and more paths are provided for the diffusion of lithium ions; meanwhile, the stability of the internal structure, the reduction of the interfacial reaction and the increase of the lithium ion diffusion path have synergistic effect, which results in the improvement of the rate performance.
3. The lithium-rich composite material provided by the embodiment of the application can be used as a positive electrode lithium supplementing material and a positive electrode active material because of more stable structure and obviously improved electrochemical properties such as cycle performance, multiplying power performance and the like of the battery, and has higher application value in manufacturing lithium ion batteries in the fields of electric automobiles, portable electronic equipment and the like.
Additional aspects and advantages of the application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
fig. 1 is a schematic structural view of a lithium-rich composite material according to an exemplary embodiment of the present application.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the lithium-rich composite of example 1 of the present application at a 200nm scale.
Fig. 3 is a Transmission Electron Microscope (TEM) image at a scale of 50nm of the lithium-rich composite of example 1 of the present application.
Fig. 4 is a Transmission Electron Microscope (TEM) image of the lithium-rich composite of example 3 of the application.
Fig. 5 is a graph showing a comparison of first charge curves of secondary batteries according to examples 1, 3 and 1 of the present application.
Fig. 6 is a graph showing the cycle performance of the secondary batteries of example 2 and comparative example 2 according to the present application.
Fig. 7 is a graph showing comparison of the rate performance of the secondary batteries of example 2 and comparative example 2 of the present application.
Reference numerals:
1-a kernel; 101-a first functional material; 2-an intermediate layer; 201-lithium-rich material; 3-an outer layer; 301-a second functional material.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present application and should not be construed as limiting the application.
In the application, unless otherwise specified, the disclosure of numerical ranges includes all values and further sub-ranges within the entire range, including the endpoints and sub-ranges given for these ranges.
In the application, the related raw materials, equipment and the like are all raw materials and equipment which can be self-made by commercial paths or known methods unless specified otherwise; the methods involved, unless otherwise specified, are all conventional.
A lithium-rich composite according to an embodiment of the present application is described below with reference to the accompanying drawings.
Fig. 1 is a schematic structural view of a lithium-rich composite material according to an exemplary embodiment of the present application.
As shown in fig. 1, the lithium-rich composite material according to the embodiment of the application includes a first functional material 101 and a lithium-rich material layer, at least a portion of the first functional material 101 is distributed inside the lithium-rich material layer; the first functional material 101 includes at least one of a first aluminum-containing compound and a first titanium-containing compound.
According to the lithium-rich composite material provided by the embodiment of the application, the first functional material contains at least one of the aluminum compound or the titanium compound, is distributed in the lithium-rich material layer, can play a role in supporting a framework, inhibits rearrangement of lithium and other non-oxygen elements in the lithium-rich material to a certain extent, and effectively improves the cycle performance of the lithium-rich composite material.
In some embodiments of the present application, the first functional material 101 and the lithium-rich material in the lithium-rich material layer are formed with a solid solution having a chemical formula of Li a Q 1-m R m O n Wherein Q includes but is not limited to at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn, R includes but is not limited to at least one of Al and Ti, and 2.ltoreq.a.ltoreq.8, 0 < m.ltoreq.0.2, 0 < n < 7. As non-limiting examples, the values of a include, but are not limited to, 2, 3, 4, 5, 6, or 8, etc., the values of m include, but are not limited to, 0.01, 0.05, 0.1, 0.15, or 0.2, etc., and the values of n include, but are not limited to, 0.1, 0.5, 1, 2, 3, 4, 5, 6, or 6.9, etc. For example, when the lithium-rich material includes Li 2 NiO 2 The first functional material comprises LiAlO 2 Due to Al 3+ With Ni 3+ The ionic radius is similar, the ionic radius and the ionic radius are easy to form solid solution, and form Li-O-Al-Ni-O bonds, so that the covalent nature of the Ni-O bonds is improved, and the internal bonding energy of the crystal is increased.
It should be noted that, when the first functional material is completely distributed inside the lithium-rich material layer, the lithium-rich composite material according to the embodiment of the present application has a two-layer structure (fig. 1 does not include the outer layer 3 and the second functional material 301), which can be understood as a material that uses the first functional material as an inner core and uses the lithium-rich material layer as a coating layer, where the first functional material plays a role of framework support, supports the lithium-rich material layer to make it difficult to collapse, and inhibits rearrangement of lithium and other non-oxygen elements in the lithium-rich material to a certain extent, thereby effectively improving the cycle performance of the lithium-rich composite material.
And when the first functional material is only partially distributed inside the lithium-rich material layer, the remaining first functional material may form the above solid solution with the lithium-rich material of the lithium-rich material layer.
In some embodiments of the present application, as shown in fig. 1, the lithium-rich composite material of the present example includes a core 1, an intermediate layer 2, and an outer layer 3 disposed in this order, where the core 1 includes at least a portion of a first functional material 101, and the intermediate layer 2 includes a lithium-rich material layer (the lithium-rich material in the lithium-rich material layer is labeled 201) and/or the solid solution described above; the outer layer 3 comprises a second functional material 301, the second functional material 301 comprising at least one of a second aluminum-containing compound, a second titanium-containing compound.
It will be appreciated that when the core comprises a portion of the first functional material and the intermediate layer comprises a layer of lithium-rich material and the remaining first functional material, the lithium-rich material in the layer of lithium-rich material forming the intermediate layer and the remaining first functional material may form a solid solution as described above.
In the embodiment of the application, the middle layer containing the lithium-rich material is arranged between the inner core and the outer layer to form a cage-shaped structure (the middle layer containing the lithium-rich material is limited in a cage formed by the inner core containing the first functional material and the outer layer containing the second functional material, and the inner core and the outer layer both contain aluminum and titanium compounds, wherein the first functional material of the inner core plays a role of supporting a framework, so that the rearrangement of lithium and other non-oxygen elements in the lithium-rich material is inhibited to a certain extent, the cycle performance of the lithium-rich material is effectively improved, and the second functional material of the outer layer can reduce the residual alkali content on the surface of the lithium-rich composite material. In addition, the volume change rate of the whole lithium-rich composite material in the charge and discharge process is low, the electrode/electrolyte reaction is reduced, the inner core element widens the lithium interlayer spacing, the defect of the lithium-rich material is increased, more paths are provided for the diffusion of lithium ions, and the conductivity of the material is improved; meanwhile, the stability of the internal structure, the reduction of the interfacial reaction and the increase of the lithium ion diffusion path have synergistic effects, which lead to the improvement of the cycle and the rate performance.
In the embodiment of the present application, the first functional material and the second functional material may be the same or different.
It is understood that in the embodiment of the present application, the first functional material 101 may be a material composed of only at least one of the first aluminum-containing compound and the first titanium-containing compound, or may be a material composed of at least one of the first aluminum-containing compound and the first titanium-containing compound and the first other component. Wherein the first additional component may include, but is not limited to, tiO 2 、Ti 2 O 3 、Li 2 TiO 3 、Al 2 O 3 、LiAlO 2 At least one of the above can restrict migration of transition metal ions and enhance structural stability. Similarly, the second functional material 301 may be a material composed of only at least one of the second aluminum-containing compound and the second titanium-containing compound, or may be a material composed of at least one of the second aluminum-containing compound and the second titanium-containing compound, and a second other component. Wherein the second other component may include, but is not limited to, tiO 2 、Ti 2 O 3 、Li 2 TiO 3 、Al 2 O 3 、LiAlO 2 At least one of the above components can eliminate residual lithium impurities, inhibit surface side reaction, and improve thermal stability.
It should be further understood that, in the embodiment of the present application, as long as the inner core 1, the intermediate layer 2 and the outer layer 3 are ensured to be sequentially disposed, the connection manner between the adjacent inner core 1, the intermediate layer 2 and the outer layer 3 and whether other material layers can be disposed in the inner core 1 are not limited, for example, the adjacent two layers of the inner core 1, the intermediate layer 2 and the outer layer 3 may be directly coated or connected through other material layers. Here, the other material layers may include, but are not limited to, at least one of lithium titanate, graphite, tin dioxide, etc., which may improve the material conductivity; when other material layers are located between the core 1 and the intermediate layer 2, the other material layers may include, but are not limited to, li 2 SiO 3 、Li 3 PO 4 、Li 2 WO 4 And LiAlO 2 At least one of the above, can enhance the interface stability and promote the migration of lithium ions; when other material layers are located between the intermediate layer 2 and the outer layer 3, the other material layers may include, but are not limited to, li 2 SiO 3 、Li 3 PO 4 、Li 2 WO 4 And LiAlO 2 At least one of the materials and the electrolyte can reduce side reaction between the materials and the electrolyte and improve stability.
In addition, in the embodiment of the present application, the outer layer is used as a coating layer of the intermediate layer, and the number of layers coated by the intermediate layer may be one or more, for example, 2 layers, 3 layers, 4 layers, or 5 layers.
As a possible example, the lithium-rich composite material of the embodiment of the present application includes an inner core 1, an intermediate layer 2, and an outer layer 3 sequentially disposed, where the inner core 1 includes a first functional material 101, and the intermediate layer 2 is a lithium-rich material layer; the outer layer 3 comprises a second functional material 301, the second functional material 301 being identical to the first functional material 101.
In some embodiments of the application, the intermediate layer 2 is coated continuously or discontinuously on the outer surface layer of the core 1. In the embodiment of the application, as described above, one of the inner cores plays a role of supporting the skeleton, so that rearrangement of lithium and other non-oxygen elements in the lithium-rich material is inhibited to a certain extent, and the cycle performance of the lithium-rich material is effectively improved. Therefore, the larger the cladding area of the intermediate layer to the core, the better the continuity, and the better the supporting effect of the core to the intermediate layer.
In some embodiments of the application, the outer layer 3 is coated continuously or discontinuously on the outer surface of the intermediate layer 2. The larger the cladding area of the outer layer is, the better the continuity is, the lower the sensitivity of the lithium-rich composite material to air is, the better the stability is, and the lower the residual alkali on the surface of the lithium-rich material is.
As non-limiting examples, the inner core 1, the intermediate layer 2 and the outer layer 3 may exist in several connection forms including, but not limited to:
(1) The middle layer 2 is continuously coated on the outer surface layer of the inner core 1, and the outer layer 3 is continuously coated on the outer surface layer of the middle layer 2 (shown in figure 1);
(2) The middle layer 2 is discontinuously coated on the outer surface layer of the inner core 1, and the outer layer 3 is continuously coated on the middle layer 2 and the outer surface layer of the inner surface layer 1 in the area which is not coated by the middle layer 2;
(3) The middle layer 2 is continuously coated on the outer surface layer of the inner core 1, and the outer layer 3 is discontinuously coated on the outer surface layer of the middle layer 2;
(4) The middle layer 2 is discontinuously coated on the outer surface layer of the inner core 1, and the outer layer 3 is discontinuously coated on the middle layer 2 and the outer surface layer of the inner surface layer 1 in the area which is not coated by the middle layer 2.
In some embodiments of the present application, the mass ratio of the inner core 1, the intermediate layer 2 and the outer layer 3 is (0.1-10) 100 (0.1-10), including but not limited to 0.1:100:0.1, 0.1:100: 10. 10:100:0.1, 10:100:10 or 5:100:5, etc. The mass ratio of the inner core to the middle layer to the outer layer is in the range, so that a good synergistic effect can be achieved to realize long circulation; beyond the above range, a certain degree of structural instability may occur during the cycling.
In some embodiments of the application, the thickness of the intermediate layer 2 is 0.5-20 μm and the thickness of the outer layer 3 is 0.05-5 μm. As non-limiting examples, the thickness of the intermediate layer 2 includes, but is not limited to, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, or 20 μm, etc., and the thickness of the outer layer 3 includes, but is not limited to, 0.05 μm, 0.1 μm, 1 μm, 2 μm, 3 μm, 5 μm, or 5 μm, etc. The thickness of the intermediate layer is in the range, so that gram capacity exertion of the lithium-rich material can be ensured, the lithium ion transmission efficiency is improved, and meanwhile, the processing performance is ensured; when the amount exceeds the above range, the lithium ion transport efficiency is low and the impedance is increased. The thickness of the outer layer is within the above range, so that the processability and the thermal stability can be ensured; beyond the above range, the gram capacity decreases.
In some embodiments of the present application, the median particle size of the first functional material 101 is less than or equal to the median particle size of the second functional material 301. The median particle size of the first functional material is less than or equal to the median particle size of the second functional material to ensure uniform distribution of the first functional material within the interior, uniformity of coating of the second functional material, and compactness. The electrochemical performance is ensured, and the stress caused by the volume expansion of the lithium-rich material can be well absorbed, so that cracks are not easy to form in the circulation process, the structure of the material is damaged, and the capacity is reduced.
As non-limiting examples, the median particle size of the first functional material 101 is 5-20nm, including but not limited to 5nm, 8nm, 11nm, 14nm, 17nm, 20nm, or the like. The median particle diameter of the first functional material 101 is within the above range, so that the skeleton supporting effect can be better achieved; when the particle size is less than 5nm, the material is easy to agglomerate, and the whole structure is difficult to realize; and if the particle size is more than 20nm, the whole structure is easy to break.
As non-limiting examples, the median particle size of the second functional material 301 is 20-100nm, including but not limited to 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, or the like. The median particle diameter of the second functional material 101 is within the above range, and a uniform and dense protective layer can be formed; less than 20nm, it is difficult to form a dense protective layer; if the thickness of the coating layer is larger than 100nm, the transmission of lithium ions is affected, and the polarization is increased.
In the embodiment of the present application, when the first functional material contains only at least one of the first aluminum-containing compound and the first titanium-containing compound, the median particle size of the first functional material is that of the at least one of the first aluminum-containing compound and the first titanium-containing compound; when the second functional material contains only at least one of the second aluminum-containing compound and the second titanium-containing compound, the median particle diameter of the second functional material, that is, the median particle diameter of at least one of the second aluminum-containing compound and the second titanium-containing compound.
In the embodiment of the present application, the first functional material 101 includes the first aluminum-containing compound or/and the first titanium-containing compound, which can restrict the migration of transition metal ions and enhance the structural stability; the second functional material contains the second aluminum-containing compound or/and the second titanium-containing compound, so that residual lithium impurities can be eliminated, surface side reactions can be inhibited, the thermal stability can be improved, and meanwhile, the storage stability and the processing stability of the lithium-rich material can be improved.
In some embodiments of the present application, the first aluminum-containing compound or/and the first titanium-containing compound in the first functional material 101 is present in an amount of 0.1 to 10wt% in the lithium-rich composite material, including, but not limited to, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, or the like. The content of the first aluminum-containing compound or/and the first titanium-containing compound in the lithium-rich composite material is within the range, so that the effect of stabilizing the structure can be achieved, and the electrochemical performance of the lithium-rich material is improved; less than 0.1wt%, no obvious effect is obtained; greater than 10wt% causes lithium ion diffusion and a decrease in electron conductivity.
When the first functional material 101 contains both the first aluminum-containing compound and the first titanium-containing compound, the first aluminum-containing compound and the first titanium-containing compound may be mixed in any mass ratio. As non-limiting examples, the mass ratio of the first aluminum-containing compound to the titanium-containing compound includes, but is not limited to, 1: (0.1-10), including but not limited to 1:0.1, 1:1:1: 3. 1: 5. 1:7 or 1:10, etc.
In some embodiments of the present application, the second aluminum-containing compound or/and the second titanium-containing compound in the second functional material 301 is present in the lithium-rich composite in an amount of 0.1-10wt%, including but not limited to 0.1wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, etc. The content of the second aluminum-containing compound or/and the second titanium-containing compound in the lithium-rich composite material is within the range, so that a compact protective layer can be formed, and the storage stability and the processing stability of the lithium-rich material are improved; less than 0.1wt%, the stability of the lithium-rich material is reduced; greater than 10wt% reduces the gram capacity of the lithium-rich material.
In some embodiments of the present application, when the first functional material 101 contains a first aluminum-containing compound and the second functional material contains a second aluminum-containing compound, the mass ratio of aluminum element in the first functional material 101 to aluminum element in the second functional material 301 is (0.2-1): 1, including but not limited to 0.2: 1. 0.3: 1. 0.4: 1. 0.5: 1. 0.6: 1. 0.7: 1. 0.8: 1. 0.9:1 or 1:1, etc. The mass ratio of the aluminum element in the first functional material 101 to the aluminum element in the second functional material 301 is in the above range, so that the lithium ion diffusion can be improved, and the storage stability and the processing stability of the lithium-rich material can be improved; less than 0.2:1wt%, the material stability is reduced; greater than 1:1, the gram capacity of the material decreases and the electron conductivity decreases. Here, when the first functional material contains aluminum in addition to the first aluminum-containing compound, the first other component contains aluminum in addition to the second aluminum-containing compound, and the second functional material contains aluminum in addition to the second aluminum-containing compound, the aluminum in the first functional material is not only aluminum in the first aluminum-containing compound but also aluminum in the entire first functional material, and the aluminum in the second functional material is not only aluminum in the second aluminum-containing compound but also aluminum in the entire second functional material; however, when the first functional material has no other aluminum element except the first aluminum-containing compound and the second functional material has no other aluminum element except the second aluminum-containing compound, the aluminum element in the first functional material is the aluminum element in the first aluminum-containing compound, and the aluminum element in the second functional material is the aluminum element in the second aluminum-containing compound.
In some embodiments of the application, the first aluminum-containing compound and the second aluminum-containing compound each include, but are not limited to, at least one of an aluminum lithium compound, an inorganic aluminum compound. Wherein the aluminum lithium compound includes, but is not limited to, liAlO 2 、Li 5 AlO 4 At least one of the following, inorganic aluminum compounds including but not limited to Al 2 O 3 、AlF 3 、AlPO 4 At least one of the following. The first aluminum-containing compound is selected from aluminum lithium compounds, inorganic aluminum compounds and the like, and can play a role of a supporting framework to improve a lithium ion diffusion channel; the second aluminum-containing compound is selected from aluminum lithium compound, inorganic aluminum compound and the like, so that the surface structure stability of the material can be improved, and the cyclic volume change of the material can be reduced.
In the embodiment of the present application, the first aluminum-containing compound and the second aluminum-containing compound may be the same or different.
As a possible example, the first functional material 101 is a first aluminum-containing compound LiAlO 2 、Li 5 AlO 4 At least one of them.
As another possible example, the first functional material 101 is a first aluminum-containing compound Al 2 O 3 、LiAlO 2 At least one of them.
In some embodiments of the application, the first titanium-containing compound and the second titanium-containing compound each include, but are not limited to, a titanium lithium compound, a titanium oxide, including, but not limited to, tiO 2 、Ti 2 O 3 、Li 4 Ti 5 O 12 、Li 2 TiO 3 、LiTi 2 (PO4) 3 At least one of the following. The first titanium-containing compound and the second titanium-containing compound are selected from the substances, so that the integrity of the microstructure and the stability of material circulation can be kept.
In the embodiment of the present application, the first titanium-containing compound and the second titanium-containing compound may be the same or different.
In some embodiments of the present application, the lithium-rich material 201 in the lithium-rich material layer includes a material having the formula Li x M y O z Is a material of (2); wherein M comprises at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn, x is more than or equal to 2 and less than or equal to 8, y is more than or equal to 0 and less than or equal to 5, and z is more than 0 and less than 7. As non-limiting examples, the values of x include, but are not limited to, 2, 3, 4, 5, 6, or 8, etc., the values of y include, but are not limited to, 0.1, 0.5, 1, 2, 3, 4, or 5, etc., and the values of z include, but are not limited to, 0.1, 0.5, 1, 2, 3, 4, 5, 6, or 6.9, etc.
As one possible example, the lithium-rich material 201 includes, but is not limited to, li 2 NiO 2 、Li 2 CuO 2 、Li 2 CoO 2 、Li 2 MnO 2 、Li 2 Ni 0.5 Mn 1.5 O 4 、Li 5 FeO 4 、Li 6 MnO 4 、Li 6 CoO 4 、Li 6 ZnO 4 At least one of the following.
In some embodiments of the present application, the lithium-rich composite further comprises an encapsulation layer, which encapsulates the outer surface of the outer layer 3; the encapsulation layer includes, but is not limited to, at least one of an isolation coating, an ion conductor coating, an electron conductor coating, a monoatomically deposited layer, an oxide nanomembrane layer.
In the embodiment of the application, each material layer such as the isolation coating layer, the ion conductor coating layer, the electronic conductor coating layer, the monoatomic deposition layer, the oxide nano film layer and the like can be coated in sequence from one side close to the outer layer to one side far away from the outer layer, and the selection of the specific material layers for coating, the sequence of coating, the thickness of coating and the like can be adjusted according to requirements.
In some embodiments of the present application, the material of the ion conductor coating layer may include at least one of perovskite type, NASICON type, garnet type. As a non-limiting example, perovskite type includes Li 3x La 2/3-x TiO 3 (LLTO), in particular Li 0.5 La 0.5 TiO 3 、Li 0.33 La 0.57 TiO 3 、Li 0.29 La 0.57 TiO 3 、Li 0.33 Ba 0.25 La 0.39 TiO 3 、(Li 0.33 La 0.56 ) 1.005 Ti 0.99 Al 0.01 O 3 、Li 0.5 La 0.5 Ti 0.95 Zr 0.05 O 3 At least one of the NASICON types such as but not limited to Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP), garnet type comprises Li 7 La 3 Zr 2 O 12 (LLZO)、Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 ，Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 At least one of the following.
In some embodiments of the application, the material of the electron conductor coating comprises at least one of a carbon material, a conductive oxide, a conductive organic. In a specific embodiment, when the material of the electronic conductor coating layer is a carbon material, the carbon material includes at least one of amorphous carbon, carbon nanotubes, graphite, carbon black, graphene, and the like. For example, when the material of the electron conductor coating layer is a carbon material, the content of the carbon material in the lithium-rich composite material ranges from 2 to 10wt%, and specifically may be 2wt%, 3wt%, 4wt%, 5wt% Typical, but non-limiting, amounts of 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, etc. In other embodiments, when the material of the electronic conductor coating is a conductive oxide, the conductive oxide may include In 2 O 3 、ZnO、SnO 2 At least one of them. The conductive organic may be a conductive polymer or the like. The electronic conductivity can be further improved by adjusting the content and the material of the electronic conductor coating layer. As detected, the positive electrode lithium-compensating additive has a resistivity of less than 5 Ω -cm at 25 ℃ in the presence of the electron conductor coating.
In some embodiments of the application, the encapsulation layer comprises 0.5-5% by mass of the entire lithium-rich composite material, and the total thickness of the encapsulation layer is 20-500nm. As non-limiting examples, the mass fraction of the encapsulation layer to the entire lithium-rich composite material includes, but is not limited to, 0.5%, 1%, 2%, 3%, 4%, or 5%, etc., and the total thickness of the encapsulation layer includes, but is not limited to, 20nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, etc. The content and thickness of the packaging layer are in the range, so that residual alkali can be eliminated, and surface side reaction can be inhibited; too high a content of the encapsulation layer and too large a thickness reduce gram capacity and conductivity.
In some embodiments of the application, the lithium-rich composite has a median particle size of 0.5 to 25.0 μm, including but not limited to 0.5 μm, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 17 μm, 20 μm, 23 μm, 25 μm, etc. The median particle diameter of the lithium-rich composite material is in the range, so that the lithium-rich composite material has good processability and dynamic performance; if the particle size is less than 0.5 μm, the specific surface area is increased, side reactions are increased, and the stability is lowered; if the particle diameter exceeds 25.0. Mu.m, the lithium ion diffusion path increases and the rate performance decreases.
In some embodiments of the application, the residual alkali content of the lithium-rich composite is less than 1500ppm, and further may be less than 1000ppm. As non-limiting examples, the residual alkali content of the lithium-rich composite includes, but is not limited to, 0, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1500ppm, and the like. The residual alkali content of the lithium-rich composite material is within the range, so that the processing performance of the lithium-rich material is better; too high a residual alkali content deteriorates processability and the lithium-rich material absorbs water easily, resulting in easy formation of jelly-like shape during homogenization. The embodiment of the application can effectively reduce the residual alkali content on the surface of the lithium-rich composite material.
In some embodiments of the application, the surface moisture content of the lithium-rich composite is less than 300ppm, further less than 200ppm. As non-limiting examples, the surface moisture content of the lithium-rich composite includes, but is not limited to, 0, 1ppm, 10ppm, 30ppm, 60ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, and the like. The surface water content of the lithium-rich composite material is in the range, so that the processing and safety performance can be ensured; when the water content is too high, the processing performance is poor, and after the battery is manufactured, the capacity, the internal resistance, the multiplying power performance and the like of the battery are attenuated to different degrees. The embodiment of the application can effectively reduce the surface water content of the lithium-rich composite material.
In some embodiments of the application, the lithium-rich composite has a volume change rate of less than 10%, further less than 7%, during charge and discharge. As non-limiting examples, the rate of change of volume of the lithium-rich composite during charge and discharge includes, but is not limited to, 0, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.9%, etc. The volume change rate of the lithium-rich composite material in the charge and discharge process is in the range, so that the lithium-rich composite material has a stable structure and good long-cycle performance; if the volume change rate is too large, the material stability becomes poor.
The preparation method of the lithium-rich composite material provided by the embodiment of the application comprises the following steps:
s101, uniformly mixing a lithium source, an M source and at least part of metal sources of the first functional material, and then sequentially performing first calcination and second calcination to obtain the lithium-rich material layer material containing the first functional material.
In some embodiments of the application, the M source is one of the sources that form the lithium-rich material, specifically the aforementioned formula Li x M y O z (2.ltoreq.x.ltoreq.8, 0.ltoreq.y.ltoreq.5, 0.ltoreq.z.ltoreq.7). Wherein the M element in the M source includes, but is not limited to, at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn. M source Including but not limited to at least one of the oxides, hydroxides, salts, and the like of the above-described M element.
As one possible example, when the M element is nickel, the M source includes, but is not limited to, niO, niCO 3 、Ni(OH) 2 At least one of the following.
In an embodiment of the present application, the first functional material metal source refers to sources of all metals contained in the first functional material in the lithium-rich composite material, and when the first functional material is at least one of the first aluminum-containing compound and the first titanium-containing compound, the first functional material metal source refers to at least one of an aluminum source of the first functional material and a titanium source of the first functional material.
In some embodiments of the application, the first functional material metal source is one of the sources from which the first functional material is formed. When the first functional material is at least one of the first aluminum-containing compound, the first titanium-containing compound, the aluminum source of the first functional material includes, but is not limited to, at least one of aluminum oxide powder, aluminum isopropoxide powder, aluminum hydroxide powder, aluminum salt powder, etc., wherein the aluminum salt includes, but is not limited to, at least one of aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum carbonate, aluminum acetate, aluminum formate, etc.; the titanium source of the first functional material includes, but is not limited to, oxides, hydroxides, salts, etc. of titanium, such as titanium dioxide, titanium hydroxide, titanium sulfate, titanium chloride, etc.
In some embodiments of the application, the lithium source is one of the sources from which the lithium-rich material is formed. The lithium source includes, but is not limited to, at least one of oxides, hydroxides, salts, and the like of lithium, such as LiOH H 2 O、LiOH、LiO 2 、Li 2 O 2 Etc.
In some embodiments of the present application, the molar ratio of the lithium element, the M element, and the metal element in the first functional material is (1.9 to 2.3): (0.9-0.99): (0.01-0.05), including but not limited to 1.9:0.9:0.01, 1.9:0.9:0.05, 1.9:0.99:0.01, 1.9:0.99:0.05, 2.3:0.9:0.01, 2.3:0.9:0.05, 2.3:0.99:0.01, 2.3:0.99:0.05 or 2.1:0.95:0.03, etc. The molar ratio of the lithium element, the M element and the metal element in the first functional material is in the range, so that the cycling stability is good, and the volume expansion rate is small; beyond the above range, the cycle performance and thermal stability are deteriorated; the surface reaction is not uniform in the charge and discharge process.
When the first functional material contains both the first aluminum-containing compound and the first titanium-containing compound, the first aluminum-containing compound and the first titanium-containing compound may be mixed in any mass ratio. As non-limiting examples, the mass ratio of the first aluminum-containing compound to the titanium-containing compound includes, but is not limited to, 1: (0.1-10).
In some embodiments of the application, the lithium source, the M source, and the first functional material metal source are mixed uniformly under an inert atmosphere using a vacuum planetary deaerator. Wherein the vacuum degree is (-100) -0Kpa, revolution rate is 0-2500rpm, rotation rate is 0-2500rpm, and mixing time is 0.5-30min. As non-limiting examples, vacuum levels include, but are not limited to, -100Kpa, -70Kpa, -50Kpa, -30Kpa, or 0, etc., revolution rates and self-transfer rates include, but are not limited to, 500rpm, 1000rpm, 1500rpm, or 2000rpm, etc., and mixing times include, but are not limited to, 5min, 10min, 15min, 20min, 25min, or 30min, etc.
In some embodiments of the application, the temperature of the first calcination is less than the temperature of the second calcination, which can allow the chemical reaction to bottom out, and the material processability and electrochemical properties are better.
Optionally, the temperature of the first calcination is 400-450 ℃, the time of the first calcination is 3-5h, and the temperature rising rate of the first calcination is 1-5 ℃/min. As non-limiting examples, the temperature of the first calcination includes, but is not limited to, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, or 450 ℃, etc., the time of the first calcination includes, but is not limited to, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours, etc., and the temperature rise rate of the first calcination includes, but is not limited to, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, or 5 ℃/min, etc.
Optionally, the temperature of the second calcination is 600-700 ℃, the time of the second calcination is 10-15h, and the temperature rising rate of the second calcination is 1-5 ℃/min. As non-limiting examples, the temperature of the second calcination includes, but is not limited to, 600 ℃, 620 ℃, 650 ℃, 670 ℃, 690 ℃, 700 ℃ or the like, the time of the second calcination includes, but is not limited to, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or the like, and the temperature rise rate of the second calcination includes, but is not limited to, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min or the like.
In some embodiments of the application, the first calcination and the second calcination may be performed in a rotary furnace, box furnace, tube furnace, roller kiln, pusher kiln, or fluidized bed, among others.
In some embodiments of the application, the method of making a lithium-rich composite includes the steps of crushing and sieving the material obtained from the second calcination after the second calcination. Thus, the product with proper particle size can be obtained, and the processing is convenient. Alternatively, the screen may be a 200-400 mesh screen, the mesh number including, but not limited to, 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, or the like.
S102, after dissolving the second functional material metal source, uniformly mixing the second functional material metal source with the material of the lithium-rich material layer containing the first functional material inside to obtain a mixed suspension.
In some embodiments of the present application, the second source of metal material is added to the organic solvent and dissolved under heating and stirring. Wherein:
the organic solvent includes, but is not limited to, at least one of small molecule alcohols (e.g., absolute ethanol, methanol, etc.), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, etc.
The volume of the organic solvent is not limited as long as the second metal material source can be completely dissolved. As one possible example, the second metal material source is aluminum isopropoxide, which is dissolved with an organic solvent, absolute ethanol, in an amount of 60-100mL.
The temperature of heating and stirring is 50-70 ℃, including but not limited to 50 ℃, 60 ℃ or 70 ℃, etc.; the heating and stirring time is 0.5-2h, including but not limited to 0.5h, 1h, 1.5h or 2h, etc.
In some embodiments of the application, the second functional material metal source is one of the sources from which the second functional material is formed. The metal source of the second functional material may be an oxide, hydroxide, salt, or the like of all metal elements in the second functional material.
As a non-limiting example, the aluminum source of the second aluminum-containing compound in the second functional material includes, but is not limited to, at least one of aluminum oxide powder, aluminum isopropoxide powder, aluminum hydroxide powder, aluminum salt powder, etc., wherein the aluminum salt includes, but is not limited to, at least one of aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum carbonate, aluminum acetate, aluminum formate, etc.
As non-limiting examples, the titanium source of the second titanium-containing compound in the second functional material includes, but is not limited to, oxides, hydroxides, salts, and the like of titanium, such as titanium dioxide, titanium hydroxide, titanium sulfate, titanium chloride, and the like.
When the second functional material contains both the second aluminum-containing compound and the second titanium-containing compound, the molar ratio of aluminum to titanium is 1:0.2-5, including but not limited to 1:0.2, 1: 1. 1: 2. 1: 3. 1:4 or 1:5, etc.
In some embodiments of the application, the mass ratio of the lithium-rich material layer material containing the first functional material to the metal source of the second functional material is (15-120): 1, including but not limited to 15: 1. 30: 1. 60: 1. 90:1 or 120:1, etc. The mass ratio of the lithium-rich material layer material containing the first functional material to the second functional material metal source is in the range, so that the processing stability and the performance stability are good; less than 15:1, processability and stability are deteriorated; greater than 120:1, the conductivity and gram capacity of the material decrease.
In some embodiments of the present application, after the second functional material metal source is dissolved, the material of the intermediate layer coated core obtained in step S101 is slowly added, and is sufficiently stirred to be uniformly mixed, so as to obtain a mixed suspension. Here, the stirring time may be 0.5 to 1h, including but not limited to 0.5h, 0.8h, 1h, or the like. The second functional material metal source is dissolved and then slowly added into the material of the intermediate layer cladding core obtained in the step S101, so that the local concentration is prevented from being too large, and the uniformity is prevented from being poor; too fast addition results in uneven dispersion and poor coating effect.
And S103, sequentially carrying out solvothermal reaction and third calcination on the mixed suspension to obtain the lithium-rich composite material.
In the embodiment of the present application, the purpose of subjecting the mixed suspension to solvothermal reaction is to form a reaction product of the material of the intermediate layer-coated core and the material of the outer layer, followed by third calcination, to form a structure of the material of the outer layer-coated intermediate layer-coated core, that is, a cage structure of the intermediate layer-coated core and the outer layer-coated intermediate layer (as shown in fig. 1).
In some embodiments of the present application, the solvent in the solvothermal reaction may employ at least one of water, absolute ethanol, isopropanol, and the like.
In some embodiments of the application, the solvothermal reaction may be carried out in a hydrothermal reaction vessel, a water bath, a polytetrafluoroethylene reaction vessel, or the like.
In some embodiments of the present application, the temperature of the solvothermal reaction may be from 100 to 140 ℃, including but not limited to 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, or the like. The solvothermal reaction temperature is within the above range, and the reaction can be completed; less than 100 ℃, the reaction is incomplete; above 140 ℃, the reaction is accelerated, the particle size distribution is widened, and the uniformity is deteriorated.
In some embodiments of the present application, the solvothermal reaction may be at a temperature for a period of 8-15 hours, including but not limited to 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, and the like. The time of the solvothermal reaction is in the range, so that the solvothermal reaction can be fully performed, and the crystallinity is better; if the reaction time is less than 8 hours, the particle size is small, and the reaction is insufficient; if the time is more than 15 hours, the particle size becomes large.
It should be noted that, in the embodiment of the present application, the temperature of the solvothermal reaction may be achieved by a heating device of the reactor itself, or may be achieved by placing the reactor in a heating apparatus, including but not limited to an oven, etc.
In some embodiments of the application, the method of preparing a lithium-rich composite further comprises the step of filtering, drying, and pulverizing the solvothermal reaction product into a powder prior to performing the third calcination.
In some embodiments of the application, the temperature of the third calcination is less than the temperature of the second calcination and less than or equal to the temperature of the first calcination.
Optionally, the temperature of the third calcination is 400-500 ℃, including but not limited to 400 ℃, 420 ℃, 450 ℃, 470 ℃, 490 ℃, 500 ℃, or the like. The third calcination temperature is in the above range, and volatile components can be removed to form a surface coating layer; the temperature is less than 400 ℃, the crystal is easy to contain impurity phases, and the crystallization performance is poor; above 500 ℃, the secondary reaction of the composite material is easy to be caused.
Optionally, the third calcination is for a period of time ranging from 1 to 5 hours, including but not limited to 1, 2, 3, 4, or 5 hours, etc. The third calcination is performed for a time within the above range, and volatile components can be removed to form a surface coating layer; if the reaction time is less than 1h, the residual alkali on the surface can be increased, and the specific surface area is reduced; if the specific surface area is larger than 5 hours, the specific surface area is increased.
In some embodiments of the application, the first calcination and the second calcination may be performed in a rotary furnace, box furnace, tube furnace, roller kiln, pusher kiln, or fluidized bed, among others.
In some embodiments of the application, the method of preparing a lithium-rich composite further comprises the step of crushing and sieving the third calcined product. Wherein the screening can be carried out by adopting a 200-400 mesh screen, and the number of the screen meshes comprises, but is not limited to, 200 meshes, 250 meshes, 300 meshes, 350 meshes or 400 meshes, etc.
It should be noted that, in the embodiment of the present application, when the lithium-rich composite material "includes the first functional material 101 and the lithium-rich material layer," all the first functional material 101 is distributed inside the lithium-rich material layer, "the preparation method of the lithium-rich composite material only includes step S101. When the lithium-rich composite material includes the inner core 1, the intermediate layer 2 and the outer layer 3, which are sequentially arranged, the inner core 1 includes the first functional material 101, the intermediate layer 2 includes the lithium-rich material layer, and the outer layer 3 includes the second functional material 301", the preparation method of the lithium-rich composite material includes step S101, step S102 and step S103, where the material obtained in step S101, that is, the material of the intermediate layer coating the inner core, is obtained.
In some embodiments of the present application, when the lithium-rich composite material further includes an encapsulation layer, and the lithium-rich composite material further includes "the first functional material 101 and the lithium-rich material layer, all of the first functional material 101 is distributed inside the lithium-rich material layer", the preparation method of the lithium-rich composite material further includes a step of mixing the material obtained in the step S101 with a source of the encapsulation layer material through a solid phase, and sintering the mixture in an inert atmosphere environment such as argon gas, to obtain the lithium-rich composite material including the encapsulation layer.
In other embodiments of the present application, when the lithium-rich composite material further includes an encapsulation layer, and the lithium-rich composite material further includes an inner core 1, an intermediate layer 2, and an outer layer 3 sequentially disposed, the inner core 1 includes a first functional material 101, the intermediate layer 2 includes a lithium-rich material layer, and the outer layer 3 includes a second functional material 301", the preparation method of the lithium-rich composite material further includes a step of mixing the material obtained in the step S103 with a source of the encapsulation layer material through a solid phase, and sintering the mixture in an inert atmosphere such as argon gas, to obtain the lithium-rich composite material including the encapsulation layer.
According to the preparation method of the lithium-rich composite material, a lithium source, an M element source in the lithium-rich material and a metal source in the first functional material are taken as raw materials, and a lithium-rich material layer material containing the first functional material inside is obtained through first calcination and second calcination (when the middle layer is the lithium-rich material layer and only contains the lithium-rich material, and the inner core only contains the first aluminum-containing compound or/and the first titanium-containing compound, the material of the lithium-rich material for coating the first aluminum-containing compound or/and the first titanium-containing compound is formed); and then, a cage-shaped lithium-rich composite material (namely, a cage-shaped lithium-rich composite material with an inner core formed by a first functional material and the like inside and an outer layer formed by a second functional material and the like outside) is obtained through solvothermal reaction and third calcination. The overall structure of the cage-shaped lithium-rich composite material is characterized in that the outermost layer is an outer layer coating layer formed by a second functional material with large particle size and the like, and the inner part is a lithium-rich material which is wrapped with an inner core formed by a first functional material with small particle size and the like. The inner core formed by the first functional material with small inner particle size plays a role in supporting a framework, so that the rearrangement of lithium and nickel is inhibited to a certain extent, and the cycle performance of the lithium-rich material is effectively improved. The outer coating layer made of the second functional material and the like is synthesized by using the lithium source remained on the surface of the material of the intermediate layer coated core after sintering. The volume change rate of the caged lithium-rich composite material in the charge and discharge processes is low, the electrode/electrolyte reaction is reduced, the conductivity of the material is improved, the defect of the lithium-rich material is increased, and more paths are provided for the diffusion of lithium ions. In addition, the stability of the internal structure thereof, the reduction of the interfacial reaction and the increase of the lithium ion diffusion path have a synergistic effect resulting in the improvement of the rate performance.
The anode comprises the lithium-rich composite material or the lithium-rich composite material prepared by the preparation method of the lithium-rich composite material.
The lithium-rich composite material of the embodiment of the application is a part of the positive electrode material in the positive electrode, and can be used as a lithium supplementing material or a positive electrode active material. When the active material is used as the positive electrode active material, it may be used alone or in combination with at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadium fluorophosphate, lithium titanate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, and the like.
In some embodiments of the present application, the lithium-rich composite material of the present examples is used as a lithium-supplementing material in an amount of 0.1 to 10wt% based on the total positive electrode material. As a non-limiting example, the lithium-rich composite material may be used as a lithium supplementing material in an amount of 0.1wt%, 0.5wt%, 1wt%, 2.5wt%, 5wt%, 7.5wt%, 10wt%, or the like based on the entire positive electrode material. The lithium-rich composite material is used as a lithium supplementing material, the content of the lithium-rich composite material accounts for the mass percent of the whole positive electrode, the lithium supplementing amount is moderate, and the energy density of the lithium ion battery can be improved; if the lithium content is less than 0.1wt%, the lithium supplementing amount is low, and the effect of improving the energy density of the lithium ion battery is not achieved; if the weight of the positive electrode material is higher than 10wt%, the ratio of the positive electrode material in the lithium ion battery is influenced, the compaction density is reduced, and the effect of improving the energy density of the lithium ion battery is not achieved even if the impedance is increased.
In other embodiments of the present application, the lithium-rich composite of the present examples is used as a positive electrode active material in an amount of 80 to 98wt% of the total positive electrode material. As a non-limiting list, the lithium-rich composite material is used as a positive electrode active material in an amount of 80wt%, 85wt%, 88wt%, 92wt% or 96wt% of the entire positive electrode material. The lithium-rich composite material is used as the positive electrode active material, the content of the lithium-rich composite material is in the range, and the lithium-rich composite material has good processing performance and capacity; below 80wt%, the energy density decreases; if the amount is more than 98% by weight, the processability becomes poor, and the requirements for the conductive agent and the binder are increased.
In some embodiments of the present application, when the lithium-rich composite material is a lithium-supplementing material, the positive electrode material may further include a positive electrode active material, and at least one of a positive electrode conductive agent, a positive electrode binder, and the like, in addition to the lithium-rich composite material. The positive electrode active material includes, but is not limited to, one or more of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadium fluorophosphate, lithium titanate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate. The positive electrode active material can perform intercalation and deintercalation, alloying and dealloying, or plating and exfoliation of lithium. Positive electrode conductive agents include, but are not limited to, one or more of graphite, carbon black, acetylene black, graphene, carbon fiber, C60, and carbon nanotubes. The positive electrode conductive agent is added into the positive electrode material to enhance the conductivity of the electrode material layer, improve the conductivity of the lithium-rich composite material and facilitate the transmission of electrons and ions. The positive electrode binder includes, but is not limited to, one or more of polyvinylidene fluoride (PVDF), sodium alginate, sodium carboxymethyl cellulose, and polyacrylic acid.
In other embodiments of the present application, when the lithium-rich composite is a positive electrode active material, the positive electrode material may further include other positive electrode active materials, and at least one of a positive electrode conductive agent, a positive electrode binder, and the like, in addition to the lithium-rich composite. Other positive electrode active materials include, but are not limited to, at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadium fluorophosphate, lithium titanate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, and the like, as previously described. The selection and function of the positive electrode conductive agent, the positive electrode binder, etc. are as described above, and will not be described again.
In some embodiments of the present application, the positive electrode further comprises a current collector, which may optionally comprise aluminum or any other suitable conductive metal foil known to those skilled in the art (such as solid or mesh or cover foil), a metal grid or mesh, or a porous metal. In certain variations, the surface of the current collector may comprise a surface treated (e.g., carbon coated and/or etched) metal foil.
The secondary battery of the embodiment of the application comprises a positive electrode, a negative electrode and a separator, wherein the positive electrode is the positive electrode of the embodiment of the application.
In some embodiments of the present application, the secondary battery includes, but is not limited to, one of a button battery, a pouch battery, and the like.
The secondary battery provided by the embodiment of the application can be widely applied to the fields of new energy power automobiles, aerospace, electronic products and the like, and particularly has higher application value in the manufacturing of lithium ion batteries in the fields of electric automobiles, portable electronic equipment, energy storage and the like.
Certain features of the present technology are further illustrated in the following non-limiting examples.
1. Examples and comparative examples
Example 1
As shown in fig. 1, the lithium-rich composite material of this embodiment includes an inner core 1, an intermediate layer 2 and an outer layer 3, where the intermediate layer 2 is continuously coated on the outer surface layer of the inner core 1, and the outer layer 3 is continuously coated on the outer surface layer of the intermediate layer 2. Wherein: the inner core 1 is LiAlO with small particle size 2 A median particle diameter (D50) of 14.9nm, the content in the lithium-rich composite material being 1% by weight; the middle layer 2 is Lithium Nickel Oxide (LNO) which is a lithium-rich material, and the Lithium Nickel Oxide (LNO) which is a lithium-rich material and LiAlO with small particle size of the inner core 1 2 Is formed with solid solution Li 2 Ni 0.92 Al 0.08 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The outer layer 3 is LiAlO with large particle size 2 A median particle diameter (D50) of 34.7nm, the content in the lithium-rich composite material being 1% by weight; the mass ratio of the inner core 1 to the middle layer 2 to the outer layer 3 is 1.05:104.6:1.05; the thickness of the middle layer 2 is 15.5um, and the thickness of the outer layer 3 is 0.1 um; the lithium-rich composite material has a median particle diameter (D50) of 16 μm, a residual alkali content of 473ppm, a surface water content of 123.3ppm, and a volume change rate during charge and discharge 5.6%.
The preparation method of the lithium-rich composite material of the embodiment comprises the following steps:
(1) Preparing a material of an intermediate layer coating core: 50.295g LIOH, 92.71g NI (OH) were weighed out separately 2 And 0.90gAl 2 O 3 Uniformly mixing in a nitrogen atmosphere by using a vacuum planetary deaeration machine (the vacuum degree is-50 Kpa, the revolution speed and the rotation speed are both 1500rpm, the mixing time is 5 min), then spreading the mixed powder in a nickel boat, putting the nickel boat into a tube furnace, sequentially carrying out first calcination and second calcination in the nitrogen atmosphere, cooling to room temperature, taking out, sieving with a 200-mesh sieve under the protection of nitrogen to obtain a material with an intermediate layer coating the inner core, and marking as an LNO/LAO material.
Wherein the temperature of the first calcination is 430 ℃, the heat preservation time (namely the time of the first calcination) is 3 hours, and the heating rate is 3 ℃/min; the temperature of the second calcination was 720 ℃, the holding time (i.e., the time of the second calcination) was 10 hours, and the rate of temperature rise from the temperature of the first calcination to the temperature of the second calcination was 5 ℃/min.
(2) Preparing a mixed suspension: 1.7g of aluminum isopropoxide is added into 50mL of absolute ethyl alcohol, heated and stirred at 60 ℃ for 1h, ultrasonic is carried out for 10min, then 30g of LNO/LAO material obtained in the step (1) is added, and stirring is continued for 30min, thus obtaining mixed suspension.
(3) Hydrothermal reaction: transferring the mixed suspension liquid obtained in the step (2) into a high-temperature reaction kettle (such as a hydrothermal reaction kettle), carrying out hydrothermal reaction for 12 hours at 120 ℃, centrifuging the mixed liquid after the reaction is finished, and putting the precipitate into a vacuum oven for drying at 70 ℃ to obtain powder of a hydrothermal reaction product.
(4) Obtaining a lithium-rich composite material: spreading the powder of the hydrothermal reaction product obtained in the step (3) in a nickel boat, putting the nickel boat into a tube furnace, heating to 425 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, performing third calcination for 4 hours, taking out and crushing the material after the material subjected to third calcination is naturally cooled to room temperature, and sieving the material with a 200-mesh sieve to obtain the caged lithium-rich composite material, wherein the caged lithium-rich composite material is marked as LNO@LAO material.
The positive electrode of the embodiment comprises a positive electrode current collector and a positive electrode material coated on the surface of the positive electrode current collector, wherein the positive electrode current collector is aluminum foil, and the positive electrode material comprises the following components in parts by weight: 1.00 parts of the lithium-rich composite material (positive electrode active material) of the embodiment, 0.10 parts of positive electrode conductive agent Super P, 0.15 parts of positive electrode binder polyvinylidene fluoride (PVDF) and 3.35 parts of positive electrode solvent N-methylpyrrolidone (NMP).
The secondary battery of the present embodiment is a button cell CR2032 including a positive electrode, a negative electrode, a separator, and an electrolyte. Wherein: the anode is the anode of the embodiment, the cathode is a metal lithium sheet, and the diaphragm adopts a Polyethylene (PE) microporous diaphragm; the electrolyte comprises Ethylene Carbonate (EC), ethylmethyl carbonate (DEC) and LiPF 6 Wherein the volume ratio of the Ethylene Carbonate (EC) to the ethylmethyl carbonate (DEC) is 3:7, liPF 6 The concentration of (C) was 1mol/L.
The preparation method of the secondary battery of the embodiment comprises the following steps:
(1) Preparing positive electrode slurry: mixing the positive electrode active substance LNO@LAO, the positive electrode binder PVDF, the positive electrode conductive agent Super p and the positive electrode solvent NMP in a formula amount by using a refiner for 10min, taking out, adding 1.00g of NMP, and continuously mixing by using the refiner for 10min to obtain the slurry of the positive electrode material.
(2) Preparing a positive electrode plate: and (3) coating the slurry of the positive electrode material obtained in the step (1) on an aluminum foil, and drying at 120 ℃ for 6 hours to prepare the positive electrode plate.
(3) And (3) forming a button cell: the positive electrode sheet, the separator, the electrolyte and the metallic lithium sheet (negative electrode) were assembled into a button cell CR2032 in a glove box.
Example 2 (lithium-rich composite as lithium supplement Material, battery was a Soft pack battery)
This embodiment is substantially the same as embodiment 1 except that:
in the positive electrode of this embodiment, the lithium-rich composite lno@lao is a positive electrode lithium supplementing material, and the positive electrode active material is lithium iron manganese phosphate (may be abbreviated as LFMP). Wherein, 94.00 parts of LFMP (positive electrode active substance), 2.00 parts of lithium-rich composite material LNO@LAO2.00 parts of positive electrode conductive agent Super P1.50 parts, 2.50 parts of positive electrode binder polyvinylidene fluoride (PVDF) and 81.82 parts of positive electrode solvent N-methylpyrrolidone (NMP).
This embodimentThe secondary battery is a soft package battery, and comprises a positive electrode, a negative electrode, a diaphragm overlapped between the positive electrode and the negative electrode in a Z shape and electrolyte, wherein: the positive electrode is the positive electrode of the embodiment; the negative electrode comprises a negative electrode current collector and a negative electrode material coated on the surface of the negative electrode current collector, wherein the negative electrode current collector is copper foil, and the negative electrode material comprises the following components in parts by weight: 95 parts of negative electrode active material graphite, 2 parts of negative electrode conductive agent Super P, 0.5 part of thickener carboxymethyl cellulose (CMC) and 2.5 parts of negative electrode binder Styrene Butadiene Rubber (SBR); the diaphragm adopts a Polyethylene (PE) microporous diaphragm; the electrolyte comprises Ethylene Carbonate (EC), ethylmethyl carbonate (DEC) and LiPF 6 Wherein the volume ratio of the Ethylene Carbonate (EC) to the ethylmethyl carbonate (DEC) is 3:7, liPF 6 The concentration of (C) was 1mol/L.
The preparation method of the secondary battery of the embodiment comprises the following steps:
1) Preparing a positive electrode: mixing the anode active material lithium iron manganese phosphate, the anode lithium supplementing material LNO@LAO, the anode conductive agent Super P, the anode binder PVDF and the anode solvent NMP according to the formula, performing ball milling and stirring to obtain anode slurry, wherein the ball milling time is 60min, the rotating speed is 30Hz, coating the anode slurry on the surface of an aluminum foil, and performing vacuum drying at 100 ℃ overnight after rolling to obtain the anode plate.
2) Preparing a negative electrode: and (3) uniformly mixing the negative electrode active material graphite, the negative electrode conductive agent Super P, the negative electrode thickener CMC and the negative electrode binder SBR according to the formula amount in deionized water to prepare negative electrode slurry, coating the negative electrode slurry on the surface of a current collector copper foil, and obtaining the negative electrode plate after the procedures of drying, rolling and secondary drying.
3) Preparing an electrolyte: mixing Ethylene Carbonate (EC) and ethylmethyl carbonate (DEC) in a volume ratio of 3:7, and adding LiPF 6 Electrolyte is formed, liPF 6 The concentration of (C) was 1mol/L.
4) Secondary battery (lithium ion battery) assembly: and assembling the lithium ion battery in a glove box in an argon inert atmosphere according to the assembling sequence of the negative electrode, the diaphragm, the electrolyte and the positive electrode.
Example 3 (aluminum-containing Compound without outer layer)
This embodiment is substantially the same as embodiment 2 except that:
the composite material of this embodiment does not comprise an outer layer 3.
The method for preparing the composite material of the present embodiment does not include steps (2) to (4).
Example 4 (lithium-rich composite core first functional Material different-titanium-containing Compound alone)
This embodiment is substantially the same as embodiment 2 except that:
in the lithium-rich composite material of the embodiment, the inner core 1 is Li with small particle size 2 TiO 3 The median particle diameter (D50) was 16.3nm.
Example 5 (lithium-rich composite core first functional Material different-aluminum-containing Compound+titanium-containing Compound)
This embodiment is substantially the same as embodiment 2 except that:
in the lithium-rich composite material of the present embodiment, the core 1 further includes Li having a small particle diameter 2 TiO 3 A median particle diameter (D50) of 15.5nm, and a content of 0.4wt% in the lithium-rich composite material; the mass ratio of the inner core 1 to the middle layer 2 to the outer layer 3 is 1.05:104.6:3.69.
In the preparation method of the lithium-rich composite material of this embodiment, 1.73g of Ti is required to be added 2 O 3 。
Example 6 (inner and outer lithium-rich composite layers differ in aluminum-containing Compounds)
This embodiment is substantially the same as embodiment 2 except that:
in the lithium-rich composite material of the embodiment, the inner core is small-particle-diameter Al 2 O 3 。
In the preparation method of the lithium-rich composite material of the embodiment, al 2 O 3 Added after the first calcination and before the second calcination.
Example 7 (inner core and outer layer of lithium-rich composite having different aluminum-containing Compound content)
This embodiment is substantially the same as embodiment 2 except that:
in the lithium-rich composite material of the embodiment, liAlO with small particle size of the inner core 1 2 The content in the lithium-rich composite material is 0.96wt%; outer layer 3 LiAlO with large particle size 2 The content in the lithium-rich composite material was 3.4wt%; the mass ratio of the inner core 1 to the middle layer 2 to the outer layer 3 is 1.05:104.6:3.69.
Example 8 (both the inner core and the outer shell contain only the titanium-containing Compound)
This embodiment is substantially the same as embodiment 2 except that:
in the lithium-rich composite material of the embodiment, the inner core 1 is Li with small particle size 2 TiO 3 A median particle diameter (D50) of 16.3nm; the outer layer 3 is Li with large particle size 2 TiO 3 The median particle diameter (D50) was 32.9nm.
In the preparation method of the present example, 1.73g of Ti was used in the step (1) 2 O 3 Replacing 0.9g Al 2 O 3 As a starting material, the first calcination temperature was 520 ℃. In the step (2), 2.7g of tetrabutyl titanate is added into 50ml of absolute ethyl alcohol, stirred for 4 hours at room temperature, and fully hydrolyzed, then 30g of the LNO/LAO material obtained in the step (1) is added, the mixture is continuously stirred for 6 hours at 45 ℃, and is obtained after filtration and drying, and is directly transferred into a tube furnace, the temperature rising rate of 3 ℃/min is increased to 500 ℃ under the nitrogen atmosphere for third calcination for 6 hours, and the temperature rising rate of 3 ℃/min is increased to 750 ℃ for fourth calcination for 10 hours. And taking out and crushing the material after the material subjected to the fourth calcination is naturally cooled to room temperature, and sieving the material with a 200-mesh sieve to obtain the cage-shaped lithium-rich composite material.
Comparative example 1
This comparative example is substantially the same as example 1 except that:
The material of the comparative example 1 is lithium nickelate, and the preparation method thereof comprises the following steps: 50.295g LiOH, 92.71g Ni (OH) were weighed out separately 2 Mixing for 10min in a vacuum planetary deaeration machine to obtain mixed powder; then spreading the mixed powder in a nickel boat, putting the nickel boat into a tube furnace, sequentially carrying out first calcination and second calcination in a nitrogen atmosphere, cooling to room temperature, taking out, and sieving with a 200-mesh sieve under the protection of nitrogen to obtain the Lithium Nickelate (LNO) material.
Wherein the temperature of the first calcination is 430 ℃, the heat preservation time (namely the time of the first calcination) is 3 hours, and the heating rate is 3 ℃/min; the temperature of the second calcination was 720 ℃, the holding time (i.e., the time of the second calcination) was 10 hours, and the rate of temperature rise from the temperature of the first calcination to the temperature of the second calcination was 5 ℃/min.
Comparative example 2
This comparative example is substantially the same as example 2 except that:
the positive electrode of this comparative example does not contain the lithium supplementing material lno@lao.
2. Performance testing
1. Topography, surface moisture content and residual alkali content testing
The morphology of each of the examples and comparative lithium-rich composites/materials was tested using Transmission Electron Microscopy (TEM), wherein the Transmission Electron Microscopy (TEM) images of the lithium-rich composites of example 1 and example 3 are shown in fig. 2-3 and fig. 4, respectively.
As can be seen from fig. 2 and 3, the surface of the lithium-rich composite particles of example 1 is rough, and the surface of Lithium Nickelate (LNO) is coated with multiple layers of LiAlO 2 Covering. The structure can effectively reduce residual alkali on the surface of Lithium Nickelate (LNO). The lno@lao surface moisture content in example 1 was tested to change from 123ppm to 300ppm only after 24 hours of air exposure, but the uncoated Lithium Nickelate (LNO) surface moisture content in comparative example 1 had exceeded 10000ppm.
As can be seen from fig. 4, example 3 lithium-rich composite particles, which did not contain an outer layer and did not undergo hydrothermal reaction and third calcination, were irregularly shaped, were smooth in surface, were mostly Al elements distributed inside LNO, and were due to Al 3+ With Ni 3+ The ionic radius is similar, the ionic radius and the ionic radius are easy to form solid solution, and Li-O-Al-Ni-O bonds are formed, so that the covalent property is improved, and the internal bonding energy of the crystal is increased.
The surface water content testing method of the lithium-rich composite material comprises the following steps: and (3) under the condition that the humidity is less than or equal to 5% RH, testing by using a coulomb moisture tester.
The method for testing the residual alkali content of the lithium-rich composite material comprises the following steps: under the condition that the humidity is less than or equal to 5 percent RH, adding the sample into absolute ethyl alcohol, stirring and filtering, taking supernatant, adding deionized water and a methyl red indicator, titrating with a hydrochloric acid standard solution, and calculating according to the volume of the consumed hydrochloric acid standard solution to obtain the residual alkali content.
2. Electrochemical performance test
(1) First charge and discharge performance
The secondary batteries of each example and comparative example were charged to 4.3V at constant current and constant voltage of 0.1C, respectively, and discharged to 2.5V at constant current, and their first charge and discharge properties were tested.
Among them, a graph comparing the first charge and discharge curves of the secondary batteries of comparative example 1, example 1 and example 2 is shown in fig. 5.
As can be seen from FIG. 5, the secondary batteries corresponding to the LNO material of comparative example 1, the LNO/LAO material of example 3 and the LNO@LNA material of example 1 respectively have specific charge capacities of 397.5mAh/g, 435.0mAh/g and 482.9mAh/g, respectively, and discharge capacities of 139.5mAh/g, 143.8mAh/g and 154.0mAh/g, respectively. Therefore, the first charge and discharge performance of the secondary battery corresponding to the LNO@LNA material in embodiment 1 of the application is obviously improved.
(2) Cycle performance
The secondary batteries of each example and comparative example were subjected to constant current charge and discharge cycle test at a rate of 2.5 to 4.25V and 1C, and were cycled for 100 cycles, and their cycle performance was examined.
The cycle performance comparison chart of example 2 and comparative example 2 is shown in fig. 6. As can be seen from fig. 6, in the first 10 cycles or so, the discharge capacity of the battery with 2% lno@lna added to the positive electrode active material of example 2 had a significant "ramp-up" phenomenon, the capacity retention rate of 100 cycles was 97.8%, while the capacity retention rate of 100 cycles of the battery with pure LFMP as the positive electrode active material of comparative example 2 was 96.1%, and the subsequent cycle curves were parallel to the pure LFMP. The positive electrode active material of the battery added with 2% LNO@LAO has the advantages that more active lithium is slowly released in the circulating process, so that the circulating performance of LFMP is improved, and the Lithium Nickelate (LNO) also contains Al 3+ It will occupy Ni 3+ Plays a framework role in the structure, effectively inhibits the phase change of the material in the circulation process, and improves the circulation performance of the material.
(3) Rate capability
The secondary batteries of each example and comparative example were subjected to rate performance test at currents of 2.5 to 4.25V, 0.1C, 0.5C, 1C, 3C, and their rate performance was examined.
Among them, a comparative graph of the rate performance of example 2 and comparative example 2 is shown in fig. 7. As can be seen from fig. 7, the specific discharge capacities of the batteries corresponding to the positive electrode active material (lfmp+2% lno@lao) of example 2 were 146.5mAh/g, 136.5mAh/g, 127.1mAh/g, and 97.8mAh/g at 0.1C, 0.5C, 1C, and 3C, respectively, and 136.3mAh/g when the rates were returned to 0.1C. As the rate increased, the specific capacity of the battery with 2% lno@lao added to the positive electrode active material of example 2 was much higher than that of the battery with pure LFMP for the positive electrode active material of comparative example 1, and the capacity recovery rate after the rate was reduced was better. This demonstrates that the lithium-rich composite lno@lao of example 2 also has a greater improvement in the rate capability of the positive electrode material. This is probably due to the fact that the lithium-rich composite material LNO@LAO with the cage-like structure is more stable, the volume change is very small in the charge and discharge process, the reaction between the electrode and the electrolyte is reduced, and meanwhile, the Lithium Nickelate (LNO) is internally provided with the catalyst due to the fact that the catalyst is prepared from the catalyst 3+ Certain defects exist in the intercalation of lithium ions, and more paths are provided for the diffusion of lithium ions.
(4) Rate of change of volume during charge and discharge
The volume change rate test method of the lithium-rich composite materials/materials of the examples and the comparative examples during charge and discharge is as follows: the unit cell volume change rate is calculated after refinement of X-ray diffraction (XRD) data.
The test results of each example and comparative example are shown in table 1.
Table 1 test results for each of examples and comparative examples
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From table 1, it can be seen that the outer layer can reduce the residual alkali of the lithium-rich material, reduce the surface moisture of the material, effectively improve the cycle stability and the rate capability of the lithium-rich material under the synergistic effect of the inner core and the outer layer, and also can obviously improve the gram capacity, the cycle and the rate capability of the LFMP when being used as a lithium supplementing material and being used in combination with the LFMP. Specifically:
as can be seen from comparative examples 1 and 2, the lithium-rich composite material of the present application can significantly improve the electrochemical performance of the battery as a lithium supplementing material, and has a lower reversible capacity fade and a better battery cycle consistency as a lithium supplementing material. In contrast, the lithium-supplementing material has better first-time charge-discharge performance and rate performance when being used as a positive electrode active material, and has better cycle performance when being used as a lithium-supplementing material.
As can be seen from comparative examples 1 and 3, the provision of the outer layer can make the lithium-rich composite material of the present application have a lower residual alkali content, surface water content and volume change rate, and can improve the first charge and discharge performance, 0.1C and 0.5C rate capability of the lithium ion battery as the positive electrode active material, but can reduce the cycle performance, 1C and 3C rate capability.
As can be seen from comparative example 2 and example 4, the inner core adopts LiAlO with small particle size on the premise that the second functional material of the outer layer is the same 2 Li with small particle size compared with the inner core 2 TiO 3 The water content of the surface is reduced by nearly half, and the first charge and discharge performance, the cycle performance and the multiplying power performance are basically equivalent.
As can be seen from comparative example 2 and example 5, the inner core adopts LiAlO with small particle size on the premise that the median particle size of the first functional material of the inner core is not greatly different and the second functional material of the outer layer is the same 2 And Li (lithium) 2 TiO 3 Compared with the LiAlO with the core which simply adopts small particle size 2 The first charge and discharge performance, the cycle performance and the rate capability are not greatly different, but the residual alkali content, the surface water content and the volume change rate are slightly increased.
As can be seen from comparative examples 2 and 6, liAlO having a large particle size was used in the outer layer 2 On the premise that the inner core adopts small-particle-size alumina compared with the inner core adopts small-particle-size LiAlO 2 The water content of the surface is slightly reduced, the residual alkali content and the volume change rate are increased, the discharge gram capacity is reduced at high multiplying power, and the cycle performance is reduced by 0.8 percent.
As can be seen from comparative example 2 and example 7, liAlO having a small particle diameter in the core 2 Reduced content and large particle size LiAlO in the outer layer 2 Under the condition of increasing the content, the content of residual alkali and the volume change rate are slightly increased, and the water content on the surface is slightly reduced; meanwhile, the cycle performance is better, and the multiplying power performance is slightly improved.
As can be seen from comparative example 2 and example 8, li is present in both the inner core and the outer layer 2 TiO 3 In the process, the residual alkali content, the surface water content and the volume change rate are all increased, and the cycle performance and the multiplying power performance are all reduced.
Compared with pure lithium nickelate, the residual alkali content, the surface water content and the volume change rate of the lithium-rich composite material are greatly reduced, and the reduction is 64.8%, 57.6% and 41.7% respectively; meanwhile, the first charge and discharge performance, the cycle performance and the multiplying power performance are greatly improved.
Compared with the comparative example 2 and the example 2, the lithium-rich composite material of the application is added in the positive electrode as a lithium supplementing material, and the residual alkali content, the surface water content, the volume change rate, the first charge and discharge performance, the cycle performance and the rate capability are obviously improved.
In conclusion, the problems of high residual alkali on the surface of the lithium-rich material for supplementing lithium, high air sensitivity and the like are solved, meanwhile, the synthesized lithium-rich composite material is more stable in structure, the electrochemical performance is obviously better than that of the lithium-rich material prepared by the prior art, the cycle performance and the multiplying power performance of the battery are obviously improved, and the lithium-rich composite material has higher application value in manufacturing lithium ion batteries in the fields of electric automobiles, energy storage, portable electronic equipment and the like.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (13)
1. The lithium-rich composite material is characterized by comprising a first functional material and a lithium-rich material layer, wherein at least part of the first functional material is distributed in the lithium-rich material layer; the first functional material comprises at least one of a first aluminum-containing compound and a first titanium-containing compound.
2. The lithium-rich composite of claim 1, wherein the lithium-rich material in the first functional material and the lithium-rich material layer forms a solid solution having a chemical formula of Li a Q 1-m R m O n Wherein Q comprises at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn, R comprises at least one of Al and Ti, a is more than or equal to 2 and less than or equal to 8, m is more than or equal to 0 and less than or equal to 0.2, and n is more than 0 and less than 7.
3. The lithium-rich composite of claim 1, comprising a core, an intermediate layer, and an outer layer disposed in sequence, the core comprising at least a portion of the first functional material, the intermediate layer comprising the layer of lithium-rich material; the outer layer includes a second functional material including at least one of a second aluminum-containing compound, a second titanium-containing compound.
4. The lithium-rich composite of claim 3, wherein the intermediate layer is coated on the outer surface of the inner core continuously or discontinuously;
and/or the outer layer is coated on the outer surface layer of the middle layer continuously or discontinuously.
5. The lithium-rich composite of claim 3, wherein the particle size of the first functional material is less than or equal to the particle size of the second functional material.
6. The lithium-rich composite of claim 3, wherein the first aluminum-containing compound and the second aluminum-containing compound each comprise at least one of an aluminum lithium compound, an inorganic aluminum compound;
and/or, the first titanium-containing compound and the second titanium-containing compound each comprise a titanium lithium compound.
7. The lithium-rich composite according to claim 3, wherein the mass ratio of the inner core to the intermediate layer to the outer layer is (0.1-10) 100 (0.1-10).
8. A lithium-rich composite according to claim 3, characterized in that the content of the first aluminum-containing compound or/and the first titanium-containing compound in the lithium-rich composite is 0.1-10wt%;
and/or the content of the second aluminum-containing compound or/and the second titanium-containing compound in the lithium-rich composite material is 0.1-10wt%;
And/or, when the first functional material contains the first aluminum-containing compound and the second functional material contains the second aluminum-containing compound, the mass ratio of aluminum element in the first functional material to aluminum element in the second functional material is (0.2-1): 1.
9. The lithium-rich composite of claim 1, wherein the lithium-rich material in the lithium-rich material layer comprises a compound of formula Li x M y O z Is a material of (2); wherein M comprises at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn, x is more than or equal to 2 and less than or equal to 8, y is more than or equal to 0 and less than or equal to 5, and z is more than 0 and less than 7;
and/or the particle size range of the lithium-rich composite material is 0.5-25.0 mu m;
and/or the residual alkali content of the lithium-rich composite material is less than 1500ppm;
and/or the surface water content of the lithium-rich composite material is less than 300ppm;
and/or the volume change rate of the lithium-rich composite material in the charge and discharge process is lower than 10%.
10. A method of preparing a lithium-rich composite according to any one of claims 1 to 9, comprising:
uniformly mixing a lithium source, an M source and at least part of metal sources of a first functional material, and then sequentially carrying out first calcination and second calcination to obtain a lithium-rich material layer material containing the first functional material inside;
The M element in the M source includes at least one of Fe, ni, mn, cu, zn, co, cr, zr, sb, ti, V, mo, sn.
11. The method of preparing a lithium-rich composite according to claim 10, further comprising:
after dissolving a second functional material metal source, uniformly mixing the dissolved second functional material metal source with the material of the lithium-rich material layer containing the first functional material inside to obtain a mixed suspension;
and sequentially carrying out solvothermal reaction and third calcination on the mixed suspension to obtain the lithium-rich composite material.
12. A positive electrode comprising the lithium-rich composite material according to any one of claims 1 to 9 or the lithium-rich composite material produced by the production method according to claim 10 or 11.
13. A secondary battery comprising a positive electrode, a negative electrode, and a separator, wherein the positive electrode is the positive electrode according to claim 12.
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