CN116404168A - Doped and coated composite modified lithium nickel manganese oxide positive electrode material and preparation method thereof - Google Patents
Doped and coated composite modified lithium nickel manganese oxide positive electrode material and preparation method thereof Download PDFInfo
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- CN116404168A CN116404168A CN202310680149.8A CN202310680149A CN116404168A CN 116404168 A CN116404168 A CN 116404168A CN 202310680149 A CN202310680149 A CN 202310680149A CN 116404168 A CN116404168 A CN 116404168A
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- manganese oxide
- lithium nickel
- nickel manganese
- nano tube
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- 239000002131 composite material Substances 0.000 title claims abstract description 103
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 186
- 239000010405 anode material Substances 0.000 claims abstract description 107
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 100
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 100
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920000767 polyaniline Polymers 0.000 claims abstract description 30
- 230000004048 modification Effects 0.000 claims abstract description 27
- 238000012986 modification Methods 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 23
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010406 cathode material Substances 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 91
- 239000008367 deionised water Substances 0.000 claims description 91
- 229910021641 deionized water Inorganic materials 0.000 claims description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 91
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 86
- 238000003756 stirring Methods 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 70
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 58
- 239000002048 multi walled nanotube Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 50
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 48
- 239000012265 solid product Substances 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 41
- 238000001914 filtration Methods 0.000 claims description 39
- 238000001291 vacuum drying Methods 0.000 claims description 33
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000007795 chemical reaction product Substances 0.000 claims description 27
- 238000004090 dissolution Methods 0.000 claims description 25
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 229940044175 cobalt sulfate Drugs 0.000 claims description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 238000010306 acid treatment Methods 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- ZVAVRBUTFWLEBK-UHFFFAOYSA-N NC1=CC(=C(C=C1)S)C1=CC=CC=C1 Chemical compound NC1=CC(=C(C=C1)S)C1=CC=CC=C1 ZVAVRBUTFWLEBK-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910001437 manganese ion Inorganic materials 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 7
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 7
- -1 mercapto, amino, carboxyl Chemical group 0.000 description 7
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 7
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 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
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DVLWCGGXLOMGRO-UHFFFAOYSA-N [Mo].[Fe].[Sr] Chemical compound [Mo].[Fe].[Sr] DVLWCGGXLOMGRO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229940008015 lithium carbonate Drugs 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- 238000002715 modification method Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Condensed Matter Physics & Semiconductors (AREA)
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a doped and coated composite modified lithium nickel manganese oxide positive electrode material and a preparation method thereof, wherein the method comprises the following steps: s1, preparing a composite modified carbon nano tube: s2, grafting iron, cerium and cobalt on the composite modified carbon nano tube to prepare a multi-metal grafted modified carbon nano tube; s3, preparing a lithium nickel manganese oxide anode material; s4, modifying the lithium nickel manganese oxide anode material by utilizing ethyl orthosilicate to prepare a surface modified anode material; s5, carrying out carbon nano tube doping and polyaniline coating composite modification treatment on the surface modified cathode material: and obtaining the doped and coated composite modified lithium nickel manganese oxide anode material. The doped and coated composite modified lithium nickel manganese oxide positive electrode material provided by the invention has higher specific discharge capacity and excellent capacity retention performance.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a doped and coated composite modified lithium nickel manganese oxide positive electrode material and a preparation method thereof.
Background
Spinel type lithium nickel manganese oxide is developed on the basis of spinel type lithium manganese oxide, and is the positive electrode material with three-dimensional lithium ion channels like lithium manganese oxide. Compared with the lithium cobalt oxide anode material, the lithium cobalt oxide anode material has high output voltage, low cost and environmental friendliness; compared with the lithium manganate anode material, the stability of the lithium manganate anode material under high-temperature circulation is greatly improved. The lithium nickel manganese oxide anode material has the advantages of high energy density, low price, environmental protection, rich resources, high voltage platform and the like, and becomes an anode material of a high specific energy power battery with good prospect. For example, a preparation method of a fourteen-sided nano nickel lithium manganate battery anode material disclosed in patent CN106898766B, a preparation method of a spherical high-voltage anode material spinel nickel lithium manganate disclosed in patent CN102569776B and the like.
However, conventional lithium nickel manganese oxide cathode materials still have some defects, such as rapid decay of the capacity of the battery for recycling, and main reasons for the defects include poor stability of the cathode materials, dissolution of manganese in the electrolyte, and the like. The patent CN103441264a discloses a method for reducing the dissolution of manganese in lithium manganate in electrolyte, which reduces the particle size of a manganese source by ball milling to slow down the dissolution of manganese ions, and still needs improvement. The modification method of the lithium ion battery lithium nickel manganese oxide material disclosed in the patent CN105720298A has the advantages that the dissolution of manganese is inhibited by coating the lithium nickel manganese oxide with strontium iron molybdenum, and a certain effect is obtained, but the discharge specific capacity performance and the capacity retention performance of the lithium ion battery nickel manganese oxide material are still required to be improved.
Therefore, there is a need in the art for improvements that provide a more reliable solution.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a doped and coated composite modified lithium nickel manganese oxide positive electrode material and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
S1, preparing a composite modified carbon nano tube:
s1-1, carrying out acid treatment on the multiwall carbon nanotubes to obtain carboxylated carbon nanotubes;
s1-2, in-situ modification of p-amino thiophenol on carboxylated carbon nanotubes to obtain composite modified carbon nanotubes;
s2, grafting iron, cerium and cobalt on the composite modified carbon nano tube to prepare a multi-metal grafted modified carbon nano tube;
s3, preparing a lithium nickel manganese oxide anode material;
s4, modifying the lithium nickel manganese oxide anode material by utilizing ethyl orthosilicate to prepare a surface modified anode material;
s5, carrying out carbon nano tube doping and polyaniline coating composite modification treatment on the surface modified cathode material:
s5-1, adding a surface modified anode material, a multi-metal grafted modified carbon nano tube and aniline into an ethanol water solution, and performing ultrasonic dispersion to obtain a solution A; adding ammonium persulfate into deionized water, and stirring for dissolution to obtain a solution B;
s5-2, dropwise adding the solution B into the solution A under the stirring state, adjusting the pH value of the obtained mixture to be acidic by using hydrochloric acid, then reacting in an inert gas atmosphere, filtering after the reaction is finished, washing a solid product, drying in vacuum, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material.
Preferably, the step S1 specifically includes:
s1-1, carrying out acid treatment on the multiwall carbon nanotube to obtain a carboxylated carbon nanotube:
adding the multiwall carbon nanotube into mixed acid of sulfuric acid and nitric acid, performing ultrasonic treatment at 65-90 ℃ for 0.5-4h, centrifuging, discarding centrifugate, washing a solid product with deionized water to be neutral, and performing vacuum drying to obtain carboxylated carbon nanotube;
s1-2, in-situ modification of p-aminophenylthiophenol on the carboxylated carbon nanotubes to obtain composite modified carbon nanotubes:
s1-2-1, adding carboxylated carbon nanotubes into hydrochloric acid, and performing ultrasonic dispersion to obtain carbon nanotube dispersion;
s1-2-2, adding p-nitrochlorobenzene into deionized water, stirring, and adding the obtained solution into a reaction kettle;
s1-2-3, adding sulfur and sodium sulfide into deionized water, and stirring to obtain a mixed solution;
s1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into the reaction kettle, performing ultrasonic dispersion, preheating to 75-120 ℃, and then dropwise adding the mixed solution obtained in the step S1-2-3 into the reaction kettle for reaction for 1-4h at 140-220 ℃;
s1-2-5, cooling the reaction product to 0-5 ℃, regulating the pH value of the reaction product to 4-6.5 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and drying in vacuum to obtain the composite modified carbon nanotube.
Preferably, the step S1-2 specifically comprises:
s1-2-1, adding 25-200mg of carboxylated carbon nanotubes into 100-400mL of hydrochloric acid with the concentration of 0.5-2mol/L, and performing ultrasonic dispersion for 30-60min to obtain carbon nanotube dispersion;
s1-2-2, adding 0.79-3.16g of p-nitrochlorobenzene into 10-40mL of deionized water, stirring for 3-10min, and adding the obtained solution into a reaction kettle;
s1-2-3, adding 0.8-3.2g of sulfur and 2-8g of sodium sulfide into 25-100mL of deionized water, and stirring to obtain a mixed solution;
s1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into the reaction kettle, performing ultrasonic dispersion for 5-30min, preheating to 75-120 ℃, dropwise adding the mixed solution obtained in the step S1-2-3 into the reaction kettle within 1-3h, and reacting for 1-4h at 140-220 ℃;
s1-2-5, cooling the reaction product to 0-5 ℃, regulating the pH value of the reaction product to 4-6.5 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and vacuum drying for 4-12h at 70-95 ℃ to obtain the composite modified carbon nanotube.
Preferably, the step S2 specifically includes:
s2-1, adding the composite modified carbon nano tube prepared in the step S1 into deionized water, then adding ferric nitrate, cobalt sulfate and cerium nitrate, performing ultrasonic dispersion to obtain a mixture, and then adjusting the pH value of the mixture to 7.5-9 by using alkali;
S2-2, transferring the mixture obtained in the step S2-1 into a reaction kettle, reacting for 3-10 hours at 150-220 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying to obtain the multi-metal grafted modified carbon nano tube.
Preferably, the step S2 specifically includes:
s2-1, adding 0.2-1g of the composite modified carbon nano tube prepared in the step S1 into 100-400mL of deionized water, then adding 20-86mg of ferric nitrate, 10-50mg of cobalt sulfate and 9-36mg of cerium nitrate, performing ultrasonic dispersion for 30-90min to obtain a mixture, and then adjusting the pH value of the mixture to 8 by using alkali;
s2-2, transferring the mixture obtained in the step S2-1 into a polytetrafluoroethylene-lined reaction kettle, reacting for 3-10 hours at 150-220 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying for 4-8 hours at 70-90 ℃ to obtain the multi-metal grafted modified carbon nano tube.
Preferably, the step S3 specifically includes:
adding a lithium source, a nickel source, a manganese source and glucose into deionized water, uniformly stirring, adding an ammonium bicarbonate aqueous solution, transferring the obtained mixture into a reaction kettle, reacting for 4-10 hours at 150-210 ℃, stirring and evaporating the reaction product at 70-100 ℃, calcining for 2-8 hours at 400-550 ℃, heating to 700-900 ℃, and calcining for 1-5 hours to obtain a lithium nickel manganese oxide anode material;
Wherein, the molar ratio of the lithium source to the nickel source to the manganese source is glucose=1.05-1.2:0.5:1.5:0.8-1.5.
Preferably, the step S4 specifically includes:
adding the lithium nickel manganese oxide positive electrode material obtained in the step S3 into an ethanol water solution, adding tetraethoxysilane, and performing ultrasonic dispersion; then ammonia water is added dropwise, stirring reaction is carried out, filtering is carried out after the reaction is finished, the solid product is washed by deionized water and ethanol in sequence, and vacuum drying is carried out, thus obtaining the surface modified anode material.
Preferably, the step S4 specifically includes:
adding 1-4g of the lithium nickel manganese oxide anode material obtained in the step S3 into 150-600mL of ethanol water solution, adding 5-20mL of ethyl orthosilicate, and performing ultrasonic dispersion for 15-60min; then dropwise adding 10-40mL of ammonia water with the concentration of 0.1-0.5mol/L, stirring and reacting for 4-14h, filtering after the reaction is finished, washing a solid product with deionized water and ethanol in sequence, and vacuum drying at 75-95 ℃ for 2-10h to obtain a surface modified anode material;
in the ethanol water solution, the volume ratio of ethanol to deionized water is 1:1.
Preferably, the step S5 specifically includes:
s5-1, adding 50-200mg of the surface modified cathode material obtained in the step S4, 4-16mg of the multi-metal grafted modified carbon nano tube and 2-10mg of aniline into 100-400mL of ethanol aqueous solution formed by mixing ethanol and deionized water according to the volume ratio of 2:1-1:3, and performing ultrasonic dispersion for 10-45min to obtain solution A; adding 6.2-24.6mg of ammonium persulfate into 10-40mL of deionized water, and stirring for dissolution to obtain a solution B;
S5-2, dropwise adding the solution B into the solution A in 15-60min under stirring, regulating the pH value of the obtained mixture to 4-5 by using hydrochloric acid, then reacting for 5-16h at 0-8 ℃ in nitrogen atmosphere, filtering after the reaction, washing a solid product, vacuum-drying for 4-12h at 80-110 ℃, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material.
The invention also provides a doped and coated composite modified lithium nickel manganese oxide anode material, which is prepared by the method.
The beneficial effects of the invention are as follows:
the doped and coated composite modified lithium nickel manganese oxide positive electrode material provided by the invention has higher specific discharge capacity and excellent capacity retention performance;
according to the invention, the multi-metal grafted modified carbon nano tube can form a crisscross conductive network, and can provide a fast transmission channel for electrons and lithium ions, so that the conductivity of the positive electrode material is improved, and the stability of the positive electrode material is improved;
according to the invention, the particle size of the anode material particles can be reduced through the coating action of polyaniline, so that the anode material particles are more uniform, and the ion diffusion is enhanced; meanwhile, the coating of polyaniline can protect the anode material, reduce the dissolution of manganese ions in electrolyte and improve the cycling stability of the battery;
In the invention, the doping of the carbon nano tube and the coating of polyaniline are carried out simultaneously, and polyaniline not only coats the anode material particles, but also coats and modifies the carbon nano tube, so that the conductivity and the dispersion performance of the carbon nano tube can be improved simultaneously; the carbon nano tube can improve the stability of the anode material by means of the chemical bond action of various functional groups (mercapto, amino, carboxyl and the like) on metal elements in the anode material while improving the conductivity of the material, and particularly can generate stronger binding/locking action on manganese ions, so that the dissolution of the manganese ions in an electrolyte is inhibited; meanwhile, the metal elements of iron, cobalt and cerium grafted on the carbon nano tube have the effect of synergistically enhancing the conductivity of the positive electrode material, and the synergistic effect of the metal elements of iron, cobalt and cerium on the carbon nano tube and polyaniline can finally ensure that the prepared positive electrode material has higher capacity and excellent cycle stability.
Drawings
FIGS. 1 and 2 are the results of cycle performance tests of the positive electrode materials prepared in example 3, comparative example 1, comparative example 2, and comparative example 4;
fig. 3 is a graph showing the results of manganese ion dissolution test of the cathode materials prepared in example 3 and comparative examples 1 to 3.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a preparation method of a doped and coated composite modified lithium nickel manganese oxide positive electrode material, which comprises the following steps:
s1, preparing a composite modified carbon nanotube, namely an F-MWCNT:
s1-1, carrying out acid treatment on the multiwall carbon nanotube to obtain a carboxylated carbon nanotube:
adding the multiwall carbon nanotube into mixed acid of sulfuric acid and nitric acid, performing ultrasonic treatment at 65-90 ℃ for 0.5-4h, centrifuging, discarding centrifugate, washing a solid product with deionized water to be neutral, and performing vacuum drying to obtain carboxylated carbon nanotube;
S1-2, in-situ modification of p-aminophenylthiophenol on carboxylated carbon nanotubes to obtain composite modified carbon nanotubes:
s1-2-1, adding 25-200mg of carboxylated carbon nanotubes into 100-400mL of hydrochloric acid with the concentration of 0.5-2mol/L, and performing ultrasonic dispersion for 30-60min to obtain carbon nanotube dispersion;
s1-2-2, adding 0.79-3.16g of p-nitrochlorobenzene into 10-40mL of deionized water, stirring for 3-10min, and adding the obtained solution into a reaction kettle;
s1-2-3, adding 0.8-3.2g of sulfur and 2-8g of sodium sulfide into 25-100mL of deionized water, and stirring to obtain a mixed solution;
s1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into a reaction kettle, performing ultrasonic dispersion for 5-30min, preheating to 75-120 ℃, and then dropwise adding the mixed solution obtained in the step S1-2-3 into the reaction kettle within 1-3h for reaction for 1-4h at 140-220 ℃;
s1-2-5, cooling the reaction product to 0-5 ℃, regulating the pH value of the reaction product to 4-6.5 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and vacuum drying for 4-12h at 70-95 ℃ to obtain the composite modified carbon nanotube.
S2, grafting iron, cerium and cobalt on the composite modified carbon nanotube to prepare the multi-metal grafted modified carbon nanotube, wherein the multi-metal grafted modified carbon nanotube is marked as F-MWCNT@Me:
s2-1, adding 0.2-1g of the composite modified carbon nano tube prepared in the step S1 into 100-400mL of deionized water, then adding 20-86mg of ferric nitrate, 10-50mg of cobalt sulfate and 9-36mg of cerium nitrate, performing ultrasonic dispersion for 30-90min to obtain a mixture, and then adjusting the pH value of the mixture to 8 by using alkali;
S2-2, transferring the mixture obtained in the step S2-1 into a polytetrafluoroethylene-lined reaction kettle, reacting for 3-10 hours at 150-220 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying for 4-8 hours at 70-90 ℃ to obtain the multi-metal grafted modified carbon nano tube.
S3, preparing a lithium nickel manganese oxide positive electrode material, namely LNMO, specifically:
adding a lithium source, a nickel source, a manganese source and glucose into deionized water, uniformly stirring, adding an ammonium bicarbonate aqueous solution, transferring the obtained mixture into a reaction kettle, reacting for 4-10 hours at 150-210 ℃, stirring and evaporating the reaction product at 70-100 ℃, calcining for 2-8 hours at 400-550 ℃, heating to 700-900 ℃ (air atmosphere), and calcining for 1-5 hours to obtain a lithium nickel manganese oxide anode material;
wherein, the molar ratio of the lithium source to the nickel source to the manganese source is glucose=1.05-1.2:0.5:1.5:0.8-1.5.
In a preferred embodiment, the lithium source, nickel source, manganese source are lithium carbonate, nickel acetate tetrahydrate, manganese acetate tetrahydrate, respectively.
S4, carrying out modification treatment on the lithium nickel manganese oxide anode material by utilizing ethyl orthosilicate to prepare a surface modified anode material, namely LNMO-TEOS, specifically comprising the following steps:
Adding 1-4g of the lithium nickel manganese oxide anode material obtained in the step S3 into 150-600mL of ethanol water solution, adding 5-20mL of ethyl orthosilicate, and performing ultrasonic dispersion for 15-60min; then dropwise adding 10-40mL of ammonia water with the concentration of 0.1-0.5mol/L, stirring and reacting for 4-14h, filtering after the reaction is finished, washing a solid product with deionized water and ethanol in sequence, and vacuum drying at 75-95 ℃ for 2-10h to obtain a surface modified anode material;
in the ethanol water solution, the volume ratio of ethanol to deionized water is 1:1.
S5, carrying out carbon nano tube doping and polyaniline coating composite modification treatment on the surface modified cathode material:
s5-1, adding 50-200mg of the surface modified cathode material obtained in the step S4, 4-16mg of the multi-metal grafted modified carbon nano tube and 2-10mg of aniline into 100-400mL of ethanol aqueous solution formed by mixing ethanol and deionized water according to the volume ratio of 2:1-1:3, and performing ultrasonic dispersion for 10-45min to obtain a solution A; adding 6.2-24.6mg of ammonium persulfate into 10-40mL of deionized water, and stirring for dissolution to obtain a solution B;
s5-2, dropwise adding the solution B into the solution A in 15-60min under stirring, regulating the pH value of the obtained mixture to 4-5 by using hydrochloric acid, then reacting for 5-16h at 0-8 ℃ in nitrogen atmosphere, filtering after the reaction, washing a solid product, vacuum-drying for 4-12h at 80-110 ℃, grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material, which is marked as F-MWCNT@Me-LNMO@PAN.
The invention also provides a doped and coated composite modified lithium nickel manganese oxide anode material, which is prepared by the method.
The main mechanism of the present invention will be described in detail below.
(1) The preparation method comprises the steps of firstly, acidizing a multi-wall carbon nano tube to form a large number of carboxyl groups on the multi-wall carbon nano tube, and then grafting a large number of p-amino thiophenol on the surface of the multi-wall carbon nano tube by adopting an in-situ synthesis method, so that abundant mercapto and amino functional groups are introduced to the surface of the multi-wall carbon nano tube; then, through in-situ deposition, grafting doping metal iron, cobalt and cerium on the multi-wall carbon nano tube, thereby obtaining the multi-metal grafting modified carbon nano tube;
carboxyl, sulfhydryl and amino introduced by the multiwall carbon nanotube can be combined with iron ions, cobalt ions and cerium ions through coordination and other actions, so that a large amount of metal ions can be uniformly loaded on the multiwall carbon nanotube, and the multiwall carbon nanotube is grafted with multiple metals.
(2) Preparing a lithium nickel manganese oxide positive electrode material by using raw materials such as a lithium source, a nickel source and a manganese source, and then modifying the lithium nickel manganese oxide positive electrode material by using ethyl orthosilicate to obtain a surface modified positive electrode material;
The surface of the lithium nickel manganese oxide anode material is coated and modified by the ethyl orthosilicate, and after the ethyl orthosilicate is hydrolyzed, siO can be coated and formed on the surface of the anode material 2 A layer for isolating and protecting the internal positive electrode material under the subsequent acidic conditionAcid corrosion resistance in the reaction process is improved, and the compactness of the anode material is improved;
in addition, the tetraethoxysilane can introduce abundant hydroxyl groups to the surface of the lithium nickel manganese oxide anode material, the hydroxyl groups are favorable for grafting a polyaniline self-assembly layer on one hand so as to promote the polyaniline to form a film on the surface of the anode material, and on the other hand, the hydroxyl groups can be combined with metal elements on the metal doped composite modified carbon nano tube so as to promote the combination between the anode material and the metal doped composite modified carbon nano tube;
(3) And finally, synchronously doping the carbon nano tube and coating polyaniline on the surface modified positive electrode material by adopting a one-step method, and finally preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material.
Wherein, the grafted metal element mainly has the following functions:
1. the reaction of doping carbon nano tube and coating modification of polyaniline on the lithium nickel manganese oxide anode material is carried out under an acidic condition, and a large amount of Fe is generated on the surface of the multi-metal grafted modified carbon nano tube under the acidic condition 3+ 、Ce 2+ 、Co 2+ Plasma, the ions can form complex/complex with hydroxyl on the surface modified cathode material, thereby promoting the surface modified cathode material to be firmly attached to the carbon nano tube;
on the other hand, fe 3+ 、Ce 2+ 、Co 2+ The plasma has stronger affinity to the amino on the aniline, can guide the aniline to be attached to the multi-metal grafted modified carbon nano tube and the anode material, and generate polyaniline coating layer by in-situ polymerization reaction, in the process, the amino in the p-aminophenylthiophenol modified on the multi-metal grafted modified carbon nano tube is combined with the aniline, and can also guide the aniline to be polymerized on the carbon nano tube regularly to generate polyaniline; namely, the metal on the carbon nano tube plays a bridging role, so that the bonding strength and coating uniformity of polyaniline on the carbon nano tube can be improved;
therefore, in the doping and polyaniline coating modification process of the lithium nickel manganese oxide anode material, the multi-metal grafted modified carbon nano tube is used as a doping component for improving the conductivity, a good reaction platform/carrier is provided for the polyaniline coating on the surface of the anode material, the coating modification of the anode material can be promoted, and further, the polyaniline also coats the multi-metal grafted modified carbon nano tube, so that the conductivity of the carbon nano tube can be further improved, and the dispersion property of the carbon nano tube is improved.
2. Particles such as Fe, co and the like can strengthen the contact between the carbon nanotubes and improve the conductivity of the carbon nanotubes;
3. the combination effect of Fe, ce and Co and hydroxyl on the surface modified anode material can promote the dispersion of the carbon nano tube in the anode material.
Wherein, the multi-metal grafting modified carbon nano tube mainly comprises the following functions: the doping of the carbon nano tube can form a crisscross conductive network, can provide a channel for fast transmission of electrons and lithium ions, improves the conductivity of the anode material, and can improve the stability of the anode material.
The coating effect of polyaniline mainly comprises: the coating can reduce the particle size of the anode material particles, so that the anode material particles are more uniform, and the ion diffusion is enhanced; meanwhile, the coating of polyaniline can protect the anode material, reduce the dissolution of manganese ions in electrolyte and improve the cycle stability of the battery.
In the invention, the doping of the carbon nano tube and the coating of polyaniline are carried out simultaneously, and polyaniline not only coats the anode material particles, but also coats and modifies the carbon nano tube, so that the conductivity and the dispersion performance of the carbon nano tube can be improved simultaneously; the carbon nano tube can improve the stability of the anode material by means of the chemical bond action of various functional groups (mercapto, amino, carboxyl and the like) on metal elements in the anode material while improving the conductivity of the material, and particularly can generate stronger binding/locking action on manganese ions, so that the dissolution of the manganese ions in an electrolyte is inhibited;
Meanwhile, the metal elements of iron, cobalt and cerium grafted on the carbon nano tube have the effect of synergistically enhancing the conductivity of the positive electrode material, and the synergistic effect of the metal elements of iron, cobalt and cerium on the carbon nano tube and polyaniline can finally ensure that the prepared positive electrode material has higher capacity, excellent multiplying power performance and cycle stability.
The foregoing is a general inventive concept and the following examples and comparative examples are provided to further illustrate the present invention.
Example 1
The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
s1, preparing a composite modified carbon nano tube F-MWCNT:
s1-1, carrying out acid treatment on the multiwall carbon nanotube to obtain a carboxylated carbon nanotube:
adding 50mg of multi-wall carbon nano tube into 100mL of mixed acid of sulfuric acid and nitric acid, carrying out ultrasonic treatment at 75 ℃ for 1.5 hours, centrifuging, discarding centrifugate, washing a solid product to be neutral by deionized water, and carrying out vacuum drying at 90 ℃ for 6 hours to obtain carboxylated carbon nano tube;
wherein, the mixed acid is obtained by mixing 98% of concentrated sulfuric acid and 72% of concentrated nitric acid according to a volume ratio of 3:1;
s1-2, in-situ modification of p-aminophenylthiophenol on carboxylated carbon nanotubes to obtain composite modified carbon nanotubes:
S1-2-1, adding 50mg of carboxylated carbon nanotubes into 200mL of hydrochloric acid with the concentration of 1mol/L, and performing ultrasonic dispersion for 45min to obtain carbon nanotube dispersion;
s1-2-2, adding 1.58g of paranitrochlorobenzene into 20mL of deionized water, stirring for 5min, and adding the obtained solution into a reaction kettle;
s1-2-3, adding 1.6g of sulfur and 4g of sodium sulfide into 50mL of deionized water, and stirring to obtain a mixed solution;
s1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into a reaction kettle, performing ultrasonic dispersion for 15min, preheating to 95 ℃, and then dropwise adding the mixed solution obtained in the step S1-2-3 into the reaction kettle within 2h for reaction for 2h at 160 ℃;
s1-2-5, cooling the reaction product to 5 ℃, adjusting the pH value of the reaction product to 6 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and drying in vacuum at 90 ℃ for 8 hours to obtain the composite modified carbon nanotube.
S2, grafting iron, cerium and cobalt on the composite modified carbon nanotube to prepare the multi-metal grafted modified carbon nanotube F-MWCNT@Me:
s2-1, adding 0.5g of the composite modified carbon nanotube prepared in the step S1 into 200mL of deionized water, then adding 43mg of ferric nitrate, 25mg of cobalt sulfate and 18mg of cerium nitrate, performing ultrasonic dispersion for 45min to obtain a mixture, and then adjusting the pH value of the mixture to 8 by using sodium hydroxide;
S2-2, transferring the mixture obtained in the step S2-1 into a polytetrafluoroethylene-lined reaction kettle, reacting for 6 hours at 180 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying for 6 hours at 90 ℃ to obtain the multi-metal grafted modified carbon nanotube.
S3, preparing a lithium nickel manganese oxide anode material LNMO, which specifically comprises the following steps:
adding the raw materials into 100mL of deionized water according to the molar ratio of lithium carbonate to nickel acetate tetrahydrate to manganese acetate tetrahydrate to glucose=1.1:0.5:1.5:1, uniformly stirring, dropwise adding 50mL of ammonium bicarbonate aqueous solution with the concentration of 0.1mol/L in a stirring state, transferring the obtained mixture into a reaction kettle, reacting for 6 hours at 190 ℃, stirring and evaporating the reaction product at 90 ℃, calcining for 4 hours at 500 ℃, heating to 780 ℃, and calcining for 2 hours to obtain the lithium nickel manganese oxide anode material.
S4, modifying the lithium nickel manganese oxide anode material by utilizing ethyl orthosilicate to prepare a surface modified anode material LNMO-TEOS, wherein the preparation method specifically comprises the following steps:
adding 2g of the lithium nickel manganese oxide anode material obtained in the step S3 into 300mL of ethanol water solution (the volume ratio of ethanol to deionized water is 1:1), adding 10mL of tetraethoxysilane, and performing ultrasonic dispersion for 30min; then 20mL of ammonia water with the concentration of 0.2mol/L is dripped, the stirring reaction is carried out for 8 hours, the filtration is carried out after the reaction is finished, the solid product is washed by deionized water and ethanol in sequence, and the vacuum drying is carried out for 6 hours at 90 ℃ to obtain the surface modified anode material.
S5, carrying out carbon nano tube doping and polyaniline coating composite modification treatment on the surface modified cathode material:
s5-1, adding 100mg of the surface modified cathode material obtained in the step S4, 8mg of the multi-metal grafted modified carbon nano tube prepared in the step S2 and 5mg of aniline into 200mL of ethanol aqueous solution prepared by mixing ethanol and deionized water according to the volume ratio of 1-2, and performing ultrasonic dispersion for 20min to obtain a solution A; adding 12.3mg of ammonium persulfate into 20mL of deionized water, and stirring for dissolution to obtain a solution B;
s5-2, dropwise adding all the solution B into the solution A in a stirring state within 30min, regulating the pH value of the obtained mixture to 4.5 by using hydrochloric acid, then reacting for 10h at 5 ℃ in nitrogen atmosphere, filtering after the reaction is finished, washing a solid product, drying for 8h at 90 ℃ in vacuum, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material: F-MWCNT@Me-LNMO@PAN.
Example 2
The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
s1, preparing a composite modified carbon nano tube F-MWCNT:
s1-1, carrying out acid treatment on the multiwall carbon nanotube to obtain a carboxylated carbon nanotube:
adding 50mg of multi-wall carbon nano tube into 100mL of mixed acid of sulfuric acid and nitric acid, carrying out ultrasonic treatment at 75 ℃ for 1.5 hours, centrifuging, discarding centrifugate, washing a solid product to be neutral by deionized water, and carrying out vacuum drying at 90 ℃ for 6 hours to obtain carboxylated carbon nano tube;
Wherein, the mixed acid is obtained by mixing 98% of concentrated sulfuric acid and 72% of concentrated nitric acid according to a volume ratio of 3:1;
s1-2, in-situ modification of p-aminophenylthiophenol on carboxylated carbon nanotubes to obtain composite modified carbon nanotubes:
s1-2-1, adding 45mg of carboxylated carbon nanotubes into 200mL of hydrochloric acid with the concentration of 1mol/L, and performing ultrasonic dispersion for 45min to obtain carbon nanotube dispersion;
s1-2-2, adding 1.58g of paranitrochlorobenzene into 20mL of deionized water, stirring for 5min, and adding the obtained solution into a reaction kettle;
s1-2-3, adding 1.6g of sulfur and 4g of sodium sulfide into 50mL of deionized water, and stirring to obtain a mixed solution;
s1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into a reaction kettle, performing ultrasonic dispersion for 15min, preheating to 90 ℃, dripping the mixed solution obtained in the step S1-2-3 into the reaction kettle within 2h, and reacting for 2h at 160 ℃;
s1-2-5, cooling the reaction product to 5 ℃, adjusting the pH value of the reaction product to 6 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and drying in vacuum at 90 ℃ for 8 hours to obtain the composite modified carbon nanotube.
S2, grafting iron, cerium and cobalt on the composite modified carbon nanotube to prepare the multi-metal grafted modified carbon nanotube F-MWCNT@Me:
S2-1, adding 0.5g of the composite modified carbon nanotube prepared in the step S1 into 200mL of deionized water, then adding 45mg of ferric nitrate, 28mg of cobalt sulfate and 16mg of cerium nitrate, performing ultrasonic dispersion for 45min to obtain a mixture, and then adjusting the pH value of the mixture to 8 by using sodium hydroxide;
s2-2, transferring the mixture obtained in the step S2-1 into a polytetrafluoroethylene-lined reaction kettle, reacting for 6 hours at 180 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying for 6 hours at 90 ℃ to obtain the multi-metal grafted modified carbon nanotube.
S3, preparing a lithium nickel manganese oxide anode material LNMO, which specifically comprises the following steps:
adding the raw materials into 100mL of deionized water according to the molar ratio of lithium carbonate to nickel acetate tetrahydrate to manganese acetate tetrahydrate to glucose=1.1:0.5:1.5:1, uniformly stirring, dropwise adding 50mL of ammonium bicarbonate aqueous solution with the concentration of 0.1mol/L in a stirring state, transferring the obtained mixture into a reaction kettle, reacting for 6 hours at 190 ℃, stirring and evaporating the reaction product at 90 ℃, calcining for 4 hours at 500 ℃, heating to 780 ℃, and calcining for 2 hours to obtain the lithium nickel manganese oxide anode material.
S4, modifying the lithium nickel manganese oxide anode material by utilizing ethyl orthosilicate to prepare a surface modified anode material LNMO-TEOS, wherein the preparation method specifically comprises the following steps:
Adding 2g of the lithium nickel manganese oxide anode material obtained in the step S3 into 300mL of ethanol water solution (the volume ratio of ethanol to deionized water is 1:1), adding 10mL of tetraethoxysilane, and performing ultrasonic dispersion for 30min; then 20mL of ammonia water with the concentration of 0.2mol/L is dripped, the stirring reaction is carried out for 8 hours, the filtration is carried out after the reaction is finished, the solid product is washed by deionized water and ethanol in sequence, and the vacuum drying is carried out for 6 hours at 90 ℃ to obtain the surface modified anode material.
S5, carrying out carbon nano tube doping and polyaniline coating composite modification treatment on the surface modified cathode material:
s5-1, adding 100mg of the surface modified cathode material obtained in the step S4, 8mg of the multi-metal grafted modified carbon nano tube prepared in the step S2 and 5mg of aniline into 200mL of ethanol aqueous solution prepared by mixing ethanol and deionized water according to the volume ratio of 1-2, and performing ultrasonic dispersion for 20min to obtain a solution A; adding 12.3mg of ammonium persulfate into 20mL of deionized water, and stirring for dissolution to obtain a solution B;
s5-2, dropwise adding all the solution B into the solution A in a stirring state within 30min, regulating the pH value of the obtained mixture to 4.5 by using hydrochloric acid, then reacting for 10h at 5 ℃ in nitrogen atmosphere, filtering after the reaction is finished, washing a solid product, drying for 8h at 90 ℃ in vacuum, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material: F-MWCNT@Me-LNMO@PAN.
Example 3
The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
s1, preparing a composite modified carbon nano tube F-MWCNT:
s1-1, carrying out acid treatment on the multiwall carbon nanotube to obtain a carboxylated carbon nanotube:
adding 50mg of multi-wall carbon nano tube into 100mL of mixed acid of sulfuric acid and nitric acid, carrying out ultrasonic treatment at 75 ℃ for 1.5 hours, centrifuging, discarding centrifugate, washing a solid product to be neutral by deionized water, and carrying out vacuum drying at 90 ℃ for 6 hours to obtain carboxylated carbon nano tube;
wherein, the mixed acid is obtained by mixing 98% of concentrated sulfuric acid and 72% of concentrated nitric acid according to a volume ratio of 3:1;
s1-2, in-situ modification of p-aminophenylthiophenol on carboxylated carbon nanotubes to obtain composite modified carbon nanotubes:
s1-2-1, adding 55mg of carboxylated carbon nanotubes into 200mL of hydrochloric acid with the concentration of 1mol/L, and performing ultrasonic dispersion for 45min to obtain carbon nanotube dispersion;
s1-2-2, adding 1.58g of paranitrochlorobenzene into 20mL of deionized water, stirring for 5min, and adding the obtained solution into a reaction kettle;
s1-2-3, adding 1.6g of sulfur and 4g of sodium sulfide into 50mL of deionized water, and stirring to obtain a mixed solution;
s1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into a reaction kettle, performing ultrasonic dispersion for 15min, preheating to 95 ℃, and then dropwise adding the mixed solution obtained in the step S1-2-3 into the reaction kettle within 2h for reaction for 2h at 160 ℃;
S1-2-5, cooling the reaction product to 5 ℃, adjusting the pH value of the reaction product to 6 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and drying in vacuum at 90 ℃ for 8 hours to obtain the composite modified carbon nanotube.
S2, grafting iron, cerium and cobalt on the composite modified carbon nanotube to prepare the multi-metal grafted modified carbon nanotube F-MWCNT@Me:
s2-1, adding 0.5g of the composite modified carbon nanotube prepared in the step S1 into 200mL of deionized water, then adding 47mg of ferric nitrate, 29mg of cobalt sulfate and 20mg of cerium nitrate, performing ultrasonic dispersion for 45min to obtain a mixture, and then adjusting the pH value of the mixture to 8 by using sodium hydroxide;
s2-2, transferring the mixture obtained in the step S2-1 into a polytetrafluoroethylene-lined reaction kettle, reacting for 6 hours at 180 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying for 6 hours at 90 ℃ to obtain the multi-metal grafted modified carbon nanotube.
S3, preparing a lithium nickel manganese oxide anode material LNMO, which specifically comprises the following steps:
adding the raw materials into 100mL of deionized water according to the molar ratio of lithium carbonate to nickel acetate tetrahydrate to manganese acetate tetrahydrate to glucose=1.1:0.5:1.5:1, uniformly stirring, dropwise adding 50mL of ammonium bicarbonate aqueous solution with the concentration of 0.1mol/L in a stirring state, transferring the obtained mixture into a reaction kettle, reacting for 6 hours at 190 ℃, stirring and evaporating the reaction product at 90 ℃, calcining for 4 hours at 500 ℃, heating to 780 ℃, and calcining for 2 hours to obtain the lithium nickel manganese oxide anode material.
S4, modifying the lithium nickel manganese oxide anode material by utilizing ethyl orthosilicate to prepare a surface modified anode material LNMO-TEOS, wherein the preparation method specifically comprises the following steps:
adding 2g of the lithium nickel manganese oxide anode material obtained in the step S3 into 300mL of ethanol water solution (the volume ratio of ethanol to deionized water is 1:1), adding 10mL of tetraethoxysilane, and performing ultrasonic dispersion for 30min; then 20mL of ammonia water with the concentration of 0.2mol/L is dripped, the stirring reaction is carried out for 8 hours, the filtration is carried out after the reaction is finished, the solid product is washed by deionized water and ethanol in sequence, and the vacuum drying is carried out for 6 hours at 90 ℃ to obtain the surface modified anode material.
S5, carrying out carbon nano tube doping and polyaniline coating composite modification treatment on the surface modified cathode material:
s5-1, adding 100mg of the surface modified cathode material obtained in the step S4, 8mg of the multi-metal grafted modified carbon nano tube prepared in the step S2 and 5mg of aniline into 200mL of ethanol aqueous solution prepared by mixing ethanol and deionized water according to the volume ratio of 1-2, and performing ultrasonic dispersion for 20min to obtain a solution A; adding 12.3mg of ammonium persulfate into 20mL of deionized water, and stirring for dissolution to obtain a solution B;
s5-2, dropwise adding all the solution B into the solution A in a stirring state within 30min, regulating the pH value of the obtained mixture to 4.5 by using hydrochloric acid, then reacting for 10h at 5 ℃ in nitrogen atmosphere, filtering after the reaction is finished, washing a solid product, drying for 8h at 90 ℃ in vacuum, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material: F-MWCNT@Me-LNMO@PAN.
Example 4
The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
s1, preparing a composite modified carbon nano tube F-MWCNT:
s1-1, carrying out acid treatment on the multiwall carbon nanotube to obtain a carboxylated carbon nanotube:
adding 50mg of multi-wall carbon nano tube into 100mL of mixed acid of sulfuric acid and nitric acid, carrying out ultrasonic treatment at 75 ℃ for 1.5 hours, centrifuging, discarding centrifugate, washing a solid product to be neutral by deionized water, and carrying out vacuum drying at 90 ℃ for 6 hours to obtain carboxylated carbon nano tube;
wherein, the mixed acid is obtained by mixing 98% of concentrated sulfuric acid and 72% of concentrated nitric acid according to a volume ratio of 3:1;
s1-2, in-situ modification of p-aminophenylthiophenol on carboxylated carbon nanotubes to obtain composite modified carbon nanotubes:
s1-2-1, adding 55mg of carboxylated carbon nanotubes into 200mL of hydrochloric acid with the concentration of 1mol/L, and performing ultrasonic dispersion for 45min to obtain carbon nanotube dispersion;
s1-2-2, adding 1.58g of paranitrochlorobenzene into 20mL of deionized water, stirring for 5min, and adding the obtained solution into a reaction kettle;
s1-2-3, adding 1.6g of sulfur and 4g of sodium sulfide into 50mL of deionized water, and stirring to obtain a mixed solution;
s1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into a reaction kettle, performing ultrasonic dispersion for 15min, preheating to 95 ℃, and then dropwise adding the mixed solution obtained in the step S1-2-3 into the reaction kettle within 2h for reaction for 2h at 160 ℃;
S1-2-5, cooling the reaction product to 5 ℃, adjusting the pH value of the reaction product to 6 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and drying in vacuum at 90 ℃ for 8 hours to obtain the composite modified carbon nanotube.
S2, grafting iron, cerium and cobalt on the composite modified carbon nanotube to prepare the multi-metal grafted modified carbon nanotube F-MWCNT@Me:
s2-1, adding 0.5g of the composite modified carbon nanotube prepared in the step S1 into 200mL of deionized water, then adding 47mg of ferric nitrate, 29mg of cobalt sulfate and 20mg of cerium nitrate, performing ultrasonic dispersion for 45min to obtain a mixture, and then adjusting the pH value of the mixture to 8 by using sodium hydroxide;
s2-2, transferring the mixture obtained in the step S2-1 into a polytetrafluoroethylene-lined reaction kettle, reacting for 6 hours at 180 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying for 6 hours at 90 ℃ to obtain the multi-metal grafted modified carbon nanotube.
S3, preparing a lithium nickel manganese oxide anode material LNMO, which specifically comprises the following steps:
adding the raw materials into 100mL of deionized water according to the molar ratio of lithium carbonate to nickel acetate tetrahydrate to manganese acetate tetrahydrate to glucose=1.1:0.5:1.5:1, uniformly stirring, dropwise adding 50mL of ammonium bicarbonate aqueous solution with the concentration of 0.1mol/L in a stirring state, transferring the obtained mixture into a reaction kettle, reacting for 6 hours at 190 ℃, stirring and evaporating the reaction product at 90 ℃, calcining for 4 hours at 500 ℃, heating to 780 ℃, and calcining for 2 hours to obtain the lithium nickel manganese oxide anode material.
S4, modifying the lithium nickel manganese oxide anode material by utilizing ethyl orthosilicate to prepare a surface modified anode material LNMO-TEOS, wherein the preparation method specifically comprises the following steps:
adding 2g of the lithium nickel manganese oxide anode material obtained in the step S3 into 300mL of ethanol water solution (the volume ratio of ethanol to deionized water is 1:1), adding 10mL of tetraethoxysilane, and performing ultrasonic dispersion for 30min; then 20mL of ammonia water with the concentration of 0.2mol/L is dripped, the stirring reaction is carried out for 8 hours, the filtration is carried out after the reaction is finished, the solid product is washed by deionized water and ethanol in sequence, and the vacuum drying is carried out for 6 hours at 90 ℃ to obtain the surface modified anode material.
S5, carrying out carbon nano tube doping and polyaniline coating composite modification treatment on the surface modified cathode material:
s5-1, adding 100mg of the surface modified cathode material obtained in the step S4, 9.5mg of the multi-metal grafted modified carbon nano tube and 7mg of aniline into 200mL of ethanol aqueous solution prepared by mixing ethanol and deionized water according to the volume ratio of 1-2, and performing ultrasonic dispersion for 20min to obtain solution A; 17.2mg of ammonium persulfate is added into 25mL of deionized water, and stirred for dissolution to obtain a solution B;
s5-2, dropwise adding all the solution B into the solution A in a stirring state within 30min, regulating the pH value of the obtained mixture to 4.5 by using hydrochloric acid, then reacting for 10h at 5 ℃ in nitrogen atmosphere, filtering after the reaction is finished, washing a solid product, drying for 8h at 90 ℃ in vacuum, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material: F-MWCNT@Me-LNMO@PAN.
Comparative example 1
The preparation method of the lithium nickel manganese oxide positive electrode material comprises the following steps:
adding the raw materials into 100mL of deionized water according to the molar ratio of lithium carbonate to nickel acetate tetrahydrate to manganese acetate tetrahydrate to glucose=1.1:0.5:1.5:1, uniformly stirring, dropwise adding 50mL of ammonium bicarbonate aqueous solution with the concentration of 0.1mol/L in a stirring state, transferring the obtained mixture into a reaction kettle, reacting for 6 hours at 190 ℃, stirring and evaporating the reaction product at 90 ℃, calcining for 4 hours at 500 ℃, heating to 780 ℃, and calcining for 2 hours to obtain a lithium nickel manganese oxide anode material: LNMO.
Comparative example 2
The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
s1, preparing carboxylated carbon nanotubes:
adding 50mg of multi-wall carbon nano tube into 100mL of mixed acid of sulfuric acid and nitric acid, carrying out ultrasonic treatment at 75 ℃ for 1.5 hours, centrifuging, discarding centrifugate, washing a solid product to be neutral by deionized water, and carrying out vacuum drying at 90 ℃ for 6 hours to obtain carboxylated carbon nano tube; wherein the mixed acid is obtained by mixing 98% of concentrated sulfuric acid and 72% of concentrated nitric acid according to a volume ratio of 3:1.
S2, preparing a lithium nickel manganese oxide anode material LNMO, which specifically comprises the following steps:
adding the raw materials into 100mL of deionized water according to the molar ratio of lithium carbonate to nickel acetate tetrahydrate to manganese acetate tetrahydrate to glucose=1.1:0.5:1.5:1, uniformly stirring, dropwise adding 50mL of ammonium bicarbonate aqueous solution with the concentration of 0.1mol/L in a stirring state, transferring the obtained mixture into a reaction kettle, reacting for 6 hours at 190 ℃, stirring and evaporating the reaction product at 90 ℃, calcining for 4 hours at 500 ℃, heating to 780 ℃, and calcining for 2 hours to obtain the lithium nickel manganese oxide anode material.
S3, carrying out carbon nano tube doping and polyaniline cladding composite modification treatment on the lithium nickel manganese oxide anode material:
s3-1, adding 100mg of the lithium nickel manganese oxide anode material obtained in the step S2, 8mg of the carboxylated carbon nanotubes prepared in the step S1 and 5mg of aniline into 200mL of ethanol aqueous solution prepared by mixing ethanol and deionized water according to the volume ratio of 1-2, and performing ultrasonic dispersion for 20min to obtain a solution A; adding 12.3mg of ammonium persulfate into 20mL of deionized water, and stirring for dissolution to obtain a solution B;
s3-2, dropwise adding all the solution B into the solution A in a stirring state within 30min, regulating the pH value of the obtained mixture to 4.5 by using hydrochloric acid, then reacting for 10h at 5 ℃ in a nitrogen atmosphere, filtering after the reaction is finished, washing a solid product, drying for 8h at 90 ℃ in vacuum, grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material, and marking as MWCNT-LNMO@PAN.
Comparative example 3
The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
s1, preparing carboxylated carbon nanotubes, wherein the specific steps are the same as those of the embodiment 3;
s2, grafting iron, cerium and cobalt on the carboxylated carbon nanotube to prepare the multi-metal grafted carbon nanotube MWCNT@Me:
S2-1, adding 0.5g of carboxylated carbon nanotubes prepared in the step S1 into 200mL of deionized water, then adding 47mg of ferric nitrate, 29mg of cobalt sulfate and 20mg of cerium nitrate, performing ultrasonic dispersion for 45min to obtain a mixture, and then adjusting the pH value of the mixture to 8 by using sodium hydroxide;
s2-2, transferring the mixture obtained in the step S2-1 into a polytetrafluoroethylene-lined reaction kettle, reacting for 6 hours at 180 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying for 6 hours at 90 ℃ to obtain the multi-metal grafted carbon nanotube MWCNT@Me.
The multi-metal grafted carbon nano tube MWCNT@Me is adopted to replace the multi-metal grafted modified carbon nano tube F-MWCNT@Me in the embodiment 3, the rest steps are the same as those in the embodiment 3, and the doped and coated composite modified lithium nickel manganese oxide anode material is finally prepared and is marked as MWCNT@Me-LNMO@PAN.
Comparative example 4
The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
s1, preparing a composite modified carbon nano tube F-MWCNT, wherein the specific steps are the same as those of the embodiment 3;
the multi-metal grafted modified carbon nanotube F-MWCNT@Me in the embodiment 3 is replaced by the composite modified carbon nanotube F-MWCNT, the rest steps are the same as those in the embodiment 3, and the doped and coated composite modified lithium nickel manganese oxide anode material is finally prepared and is marked as F-MWCNT-LNMO@PAN.
Comparative example 5
The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material comprises the following steps:
s1, preparing a composite modified carbon nano tube F-MWCNT, wherein the specific steps are the same as those of the embodiment 3;
s2, grafting iron, cerium and cobalt on the composite modified carbon nano tube to prepare the multi-metal grafted modified carbon nano tube F-MWCNT@Me, wherein the specific steps are the same as those of the embodiment 3;
s3, preparing a lithium nickel manganese oxide anode material LNMO, wherein the specific steps are the same as those of the embodiment 3;
s4, carrying out carbon nano tube doping and polyaniline cladding composite modification treatment on the lithium nickel manganese oxide anode material:
s5-1, adding 100mg of the lithium nickel manganese oxide anode material obtained in the step S4, 8mg of the multi-metal grafted modified carbon nano tube prepared in the step S2 and 5mg of aniline into 200mL of ethanol aqueous solution prepared by mixing ethanol and deionized water according to the volume ratio of 1-2, and performing ultrasonic dispersion for 20min to obtain a solution A; adding 12.3mg of ammonium persulfate into 20mL of deionized water, and stirring for dissolution to obtain a solution B;
s5-2, dropwise adding all the solution B into the solution A in a stirring state for 30min, regulating the pH value of the obtained mixture to 4.5 by using hydrochloric acid, then reacting for 10h at 5 ℃ in a nitrogen atmosphere, filtering after the reaction is finished, washing a solid product, drying for 8h at 90 ℃ in vacuum, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material which is marked as F-MWCNT@Me LNMO@PAN'.
Performance testing was performed as follows:
(1) The positive electrode materials prepared in examples 1 to 4 and comparative examples 1 to 5 were assembled into button cells as follows, respectively, and charge and discharge tests were performed as follows:
and (3) battery assembly: mixing a positive electrode material, conductive carbon black and polyvinylidene fluoride according to a mass ratio of 75:15:10 to prepare slurry, coating the slurry on an aluminum foil, and drying to prepare a positive electrode plate; liPF with metallic lithium sheet as negative electrode, polypropylene film (Gelgard 2300) as separator, 1mol/L 6 The ethylene carbonate and dimethyl carbonate solution (the volume ratio of the ethylene carbonate to the dimethyl carbonate is 1:1) is taken as electrolyte to assemble the CR2032 button cell;
and (3) charge and discharge testing: and (3) performing charge and discharge tests on a Land charge and discharge tester, wherein the current density is 0.2 ℃, the voltage range of the test is 2.0-4.0V, the cycle is 50 weeks, and the test temperature is 25 ℃.
Table 1 below shows the initial discharge specific capacities at 0.2C and the capacity retention rates after 50 weeks of the coin cells assembled from the positive electrode materials of examples 1 to 4 and comparative examples 1 to 5.
TABLE 1
As can be seen from the detection results of table 1, the batteries assembled from the cathode materials of examples 1 to 4 have a higher specific discharge capacity and excellent capacity retention performance; in comparative example 1, the lithium nickel manganese oxide positive electrode material was not modified, and the performance was most severely degraded; in comparative example 2, the performance is obviously reduced by directly doping the carboxyl carbon nano tube; the carbon nanotubes in comparative example 3 were not subjected to sulfanilic acid modification, and the overall was significantly different from examples 1 to 4; the carbon nanotubes in comparative example 4 were not grafted with metal elements, and the overall performance was lowered; the specific discharge capacity and capacity retention performance in comparative example 5 were slightly degraded due to the fact that the lithium nickel manganese oxide positive electrode material was not subjected to TEOS modification treatment.
Referring to fig. 1 and 2, the cycle performance test results (current density 0.2C) of example 3, comparative example 1, comparative example 2 and comparative example 4 are shown in fig. 1, which is a graph of discharge specific capacitance retention versus cycle number, and fig. 2, which is a graph of capacity retention versus cycle number; it can be seen that example 3 has significantly better cycling stability than the three comparative examples.
(2) Dissolution performance test of manganese ions:
to further illustrate the present invention, the positive electrode materials prepared in example 3 and comparative examples 1 to 3 were immersed in an electrolyte solution at 50℃in which 0.1g of the positive electrode material, 25mL of the electrolyte solution, and 1mol/L of LiPF were used 6 Vinyl carbonate and dimethyl carbonate solution (the volume ratio of the vinyl carbonate to the dimethyl carbonate is 1:1); detection of Mn in electrolyte solutions at different soaking times using Atomic Absorption Spectroscopy (AAS) 2+ Concentration of (i.e. Mn) 2+ The amount of dissolution) of the sample is shown in FIG. 3.
As can be seen from the detection results of fig. 3, the inhibition effect of example 3 on manganese ion dissolution is significantly better than other comparative examples, and in comparative example 1, no modification treatment is performed on the lithium nickel manganese oxide positive electrode material, so that manganese ion dissolution is the most serious; in comparative example 2, the effect of inhibiting dissolution of manganese ions is remarkably reduced by directly doping the carboxyl carbon nanotubes; in comparative example 3, the carbon nanotubes were not modified with sulfanilic acid, and the effect of inhibiting dissolution of manganese ions was also inferior to that of example 3.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The preparation method of the doped and coated composite modified lithium nickel manganese oxide positive electrode material is characterized by comprising the following steps of:
s1, preparing a composite modified carbon nano tube:
s1-1, carrying out acid treatment on the multiwall carbon nanotubes to obtain carboxylated carbon nanotubes;
s1-2, in-situ modification of p-amino thiophenol on carboxylated carbon nanotubes to obtain composite modified carbon nanotubes;
s2, grafting iron, cerium and cobalt on the composite modified carbon nano tube to prepare a multi-metal grafted modified carbon nano tube;
s3, preparing a lithium nickel manganese oxide anode material;
s4, modifying the lithium nickel manganese oxide anode material by utilizing ethyl orthosilicate to prepare a surface modified anode material;
s5, carrying out carbon nano tube doping and polyaniline coating composite modification treatment on the surface modified cathode material:
S5-1, adding a surface modified anode material, a multi-metal grafted modified carbon nano tube and aniline into an ethanol water solution, and performing ultrasonic dispersion to obtain a solution A; adding ammonium persulfate into deionized water, and stirring for dissolution to obtain a solution B;
s5-2, dropwise adding the solution B into the solution A under the stirring state, adjusting the pH value of the obtained mixture to be acidic by using hydrochloric acid, then reacting in an inert gas atmosphere, filtering after the reaction is finished, washing a solid product, drying in vacuum, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material.
2. The method for preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material according to claim 1, wherein the step S1 is specifically:
s1-1, carrying out acid treatment on the multiwall carbon nanotube to obtain a carboxylated carbon nanotube:
adding the multiwall carbon nanotube into mixed acid of sulfuric acid and nitric acid, performing ultrasonic treatment at 65-90 ℃ for 0.5-4h, centrifuging, discarding centrifugate, washing a solid product with deionized water to be neutral, and performing vacuum drying to obtain carboxylated carbon nanotube;
s1-2, in-situ modification of p-aminophenylthiophenol on the carboxylated carbon nanotubes to obtain composite modified carbon nanotubes:
s1-2-1, adding carboxylated carbon nanotubes into hydrochloric acid, and performing ultrasonic dispersion to obtain carbon nanotube dispersion;
S1-2-2, adding p-nitrochlorobenzene into deionized water, stirring, and adding the obtained solution into a reaction kettle;
s1-2-3, adding sulfur and sodium sulfide into deionized water, and stirring to obtain a mixed solution;
s1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into the reaction kettle, performing ultrasonic dispersion, preheating to 75-120 ℃, and then dropwise adding the mixed solution obtained in the step S1-2-3 into the reaction kettle for reaction for 1-4h at 140-220 ℃;
s1-2-5, cooling the reaction product to 0-5 ℃, regulating the pH value of the reaction product to 4-6.5 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and drying in vacuum to obtain the composite modified carbon nanotube.
3. The method for preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material according to claim 2, wherein the step S1-2 is specifically:
s1-2-1, adding 25-200mg of carboxylated carbon nanotubes into 100-400mL of hydrochloric acid with the concentration of 0.5-2mol/L, and performing ultrasonic dispersion for 30-60min to obtain carbon nanotube dispersion;
s1-2-2, adding 0.79-3.16g of p-nitrochlorobenzene into 10-40mL of deionized water, stirring for 3-10min, and adding the obtained solution into a reaction kettle;
s1-2-3, adding 0.8-3.2g of sulfur and 2-8g of sodium sulfide into 25-100mL of deionized water, and stirring to obtain a mixed solution;
S1-2-4, adding the carbon nano tube dispersion liquid obtained in the step S1-2-1 into the reaction kettle, performing ultrasonic dispersion for 5-30min, preheating to 75-120 ℃, dropwise adding the mixed solution obtained in the step S1-2-3 into the reaction kettle within 1-3h, and reacting for 1-4h at 140-220 ℃;
s1-2-5, cooling the reaction product to 0-5 ℃, regulating the pH value of the reaction product to 4-6.5 by using hydrochloric acid, filtering, washing the solid product by using ethanol, and vacuum drying for 4-12h at 70-95 ℃ to obtain the composite modified carbon nanotube.
4. The method for preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material according to claim 1, wherein the step S2 is specifically:
s2-1, adding the composite modified carbon nano tube prepared in the step S1 into deionized water, then adding ferric nitrate, cobalt sulfate and cerium nitrate, performing ultrasonic dispersion to obtain a mixture, and then adjusting the pH value of the mixture to 7.5-9 by using alkali;
s2-2, transferring the mixture obtained in the step S2-1 into a reaction kettle, reacting for 3-10 hours at 150-220 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying to obtain the multi-metal grafted modified carbon nano tube.
5. The method for preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material according to claim 4, wherein the step S2 is specifically:
S2-1, adding 0.2-1g of the composite modified carbon nano tube prepared in the step S1 into 100-400mL of deionized water, then adding 20-86mg of ferric nitrate, 10-50mg of cobalt sulfate and 9-36mg of cerium nitrate, performing ultrasonic dispersion for 30-90min to obtain a mixture, and then adjusting the pH value of the mixture to 8 by using alkali;
s2-2, transferring the mixture obtained in the step S2-1 into a polytetrafluoroethylene-lined reaction kettle, reacting for 3-10 hours at 150-220 ℃, cooling to room temperature after the reaction is finished, filtering, washing a solid product with deionized water, and vacuum drying for 4-8 hours at 70-90 ℃ to obtain the multi-metal grafted modified carbon nano tube.
6. The method for preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material according to claim 1, wherein the step S3 is specifically:
adding a lithium source, a nickel source, a manganese source and glucose into deionized water, uniformly stirring, adding an ammonium bicarbonate aqueous solution, transferring the obtained mixture into a reaction kettle, reacting for 4-10 hours at 150-210 ℃, stirring and evaporating the reaction product at 70-100 ℃, calcining for 2-8 hours at 400-550 ℃, heating to 700-900 ℃, and calcining for 1-5 hours to obtain a lithium nickel manganese oxide anode material;
wherein, the molar ratio of the lithium source to the nickel source to the manganese source is glucose=1.05-1.2:0.5:1.5:0.8-1.5.
7. The method for preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material according to claim 1, wherein the step S4 is specifically:
adding the lithium nickel manganese oxide positive electrode material obtained in the step S3 into an ethanol water solution, adding tetraethoxysilane, and performing ultrasonic dispersion; then ammonia water is added dropwise, stirring reaction is carried out, filtering is carried out after the reaction is finished, the solid product is washed by deionized water and ethanol in sequence, and vacuum drying is carried out, thus obtaining the surface modified anode material.
8. The method for preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material according to claim 7, wherein the step S4 is specifically:
adding 1-4g of the lithium nickel manganese oxide anode material obtained in the step S3 into 150-600mL of ethanol water solution, adding 5-20mL of ethyl orthosilicate, and performing ultrasonic dispersion for 15-60min; then dropwise adding 10-40mL of ammonia water with the concentration of 0.1-0.5mol/L, stirring and reacting for 4-14h, filtering after the reaction is finished, washing a solid product with deionized water and ethanol in sequence, and vacuum drying at 75-95 ℃ for 2-10h to obtain a surface modified anode material;
in the ethanol water solution, the volume ratio of ethanol to deionized water is 1:1.
9. The method for preparing the doped and coated composite modified lithium nickel manganese oxide positive electrode material according to claim 8, wherein the step S5 is specifically:
S5-1, adding 50-200mg of the surface modified cathode material obtained in the step S4, 4-16mg of the multi-metal grafted modified carbon nano tube and 2-10mg of aniline into 100-400mL of ethanol aqueous solution formed by mixing ethanol and deionized water according to the volume ratio of 2:1-1:3, and performing ultrasonic dispersion for 10-45min to obtain solution A; adding 6.2-24.6mg of ammonium persulfate into 10-40mL of deionized water, and stirring for dissolution to obtain a solution B;
s5-2, dropwise adding the solution B into the solution A in 15-60min under stirring, regulating the pH value of the obtained mixture to 4-5 by using hydrochloric acid, then reacting for 5-16h at 0-8 ℃ in nitrogen atmosphere, filtering after the reaction, washing a solid product, vacuum-drying for 4-12h at 80-110 ℃, and grinding to obtain the doped and coated composite modified lithium nickel manganese oxide anode material.
10. A doped, coated composite modified lithium nickel manganese oxide positive electrode material, characterized in that it is prepared by the method according to any one of claims 1-9.
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Citations (5)
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| CN103996844A (en) * | 2014-05-26 | 2014-08-20 | 东莞市迈科科技有限公司 | Composite lithium nickel manganese oxide positive electrode material and preparation method thereof |
| CN105226267A (en) * | 2015-08-25 | 2016-01-06 | 武汉理工大学 | Three dimensional carbon nanotubes modifies spinel nickel lithium manganate material and its preparation method and application |
| CN108183209A (en) * | 2017-12-25 | 2018-06-19 | 昆明高聚科技有限公司 | A kind of polyaniline-coated method of modifying of nickel-cobalt lithium manganate cathode material |
| CN110943220A (en) * | 2019-12-13 | 2020-03-31 | 河南科技学院 | Lithium ion power battery composite positive electrode material and preparation method thereof |
| CN115571929A (en) * | 2022-12-07 | 2023-01-06 | 深圳中芯能科技有限公司 | Nickel-manganese binary composite positive electrode material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996844A (en) * | 2014-05-26 | 2014-08-20 | 东莞市迈科科技有限公司 | Composite lithium nickel manganese oxide positive electrode material and preparation method thereof |
| CN105226267A (en) * | 2015-08-25 | 2016-01-06 | 武汉理工大学 | Three dimensional carbon nanotubes modifies spinel nickel lithium manganate material and its preparation method and application |
| CN108183209A (en) * | 2017-12-25 | 2018-06-19 | 昆明高聚科技有限公司 | A kind of polyaniline-coated method of modifying of nickel-cobalt lithium manganate cathode material |
| CN110943220A (en) * | 2019-12-13 | 2020-03-31 | 河南科技学院 | Lithium ion power battery composite positive electrode material and preparation method thereof |
| CN115571929A (en) * | 2022-12-07 | 2023-01-06 | 深圳中芯能科技有限公司 | Nickel-manganese binary composite positive electrode material and preparation method thereof |
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