CN109980213A - The excellent layered oxide cell positive material of air stability and its method for constructing gradient-structure raising material air stability - Google Patents
The excellent layered oxide cell positive material of air stability and its method for constructing gradient-structure raising material air stability Download PDFInfo
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- CN109980213A CN109980213A CN201910336241.6A CN201910336241A CN109980213A CN 109980213 A CN109980213 A CN 109980213A CN 201910336241 A CN201910336241 A CN 201910336241A CN 109980213 A CN109980213 A CN 109980213A
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000000470 constituent Substances 0.000 claims abstract description 21
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 16
- 238000000975 co-precipitation Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000011734 sodium Substances 0.000 claims description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002482 conductive additive Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- -1 transition metal salt Chemical class 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006245 Carbon black Super-P Substances 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000005486 organic electrolyte Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052789 astatine Inorganic materials 0.000 claims 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 39
- 239000010405 anode material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000002344 surface layer Substances 0.000 description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 18
- 229910001415 sodium ion Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 241000080590 Niso Species 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910018434 Mn0.5O2 Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- 229910018970 NaNi0.5Mn0.5O2 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910011681 LiNi0.7Co0.2Al0.1O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910014507 Na0.67Ni0.33Mn0.67O2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical group O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the excellent layered oxide cell positive material of air stability and its methods for constructing gradient-structure raising material air stability.Pass through coprecipitation, synthesis has chondritic particulate alkali metal ion battery anode layered oxide, pass through regulation particle kernel to the ratio of chemical constituents different between shell, wherein kernel is high electrochemical component, shell is the good component of air stability, and then obtains electrochemistry and all excellent electrode anode material of air stability.Therefore alkali metal ion stratiform cell positive material of the invention can be provided new opinion to the optimization design of high performance alkali metal-ion battery anode stratified material, be had broad application prospects by the modulation in the synthesis process to chemical constituent in particle.
Description
Technical field
The invention belongs to field of electrochemical power source, and in particular to the excellent layered oxide battery of a kind of air stability is just
Pole material and its method for constructing gradient-structure raising material air stability.
Background technique
Tight demand due to modern society to the utilization of renewable energy and the popularization of smart grid, bulk electrochemical storage
The demand of energy system has been a great concern in past many decades.Alkali metal-ion battery is since energy density is high, follows
The advantages that ring service life is long is in energy storage field in occupation of particularly important status.
In recent years, alkali metal-ion battery laminate oxide anode material is due to reversible removal lithium embedded, sodium ion etc.
Crystal structure, specific capacity is high, preparation method is simple and a series of advantages such as cheap, so that it is obtained the section of energy storage field
The further investigation of scholars becomes the focus being concerned.
However, since layered oxide positive electrode air stability is poor, so that such material is badly in need of setting after the preparation
It is protected in the environment of being full of inert gas.Which results in transport, the application of such material in the actual production process
It is greatly limited.Therefore, become by a kind of method for finding feasible such material air stability of raising and pushed
The key that alkali metal-ion battery further develops.
In view of the above problems, the present invention utilizes different metal doped alkali metal ion battery anode layer by coprecipitation
Shape oxide synthesizes the particle with chondritic, by regulating and controlling the ratio of particle kernel to chemical constituents different between shell,
Middle kernel is high electrochemical component, and shell is the good component of air stability, and then acquisition electrochemistry and air stability are all excellent
Electrode material.
Summary of the invention
The object of the present invention is to provide the excellent layered oxide cell positive material of air stability and its construct gradient
The method of structure raising material air stability.
Present invention firstly provides a kind of air stability is excellent, there is gradient gradually to chemical constituent between shell inside particle
The layered oxide positive electrode A of changexBO2(kernel)-AxMO2(shell), wherein A be alkali metal, preferably Li, Na, K, into one
Step is preferably Li, Na, and B is selected from the transition metal with electro-chemical activity, preferably at least one of Fe, Co, Ni, Mn, V, Cr,
Further preferably Fe, Co, Ni, Mn；M is the excellent element composition of air stability, and the M is in Cu, Li, Mg, Ca, Ba
At least one, wherein 0.6≤x≤2, preferably 0.67≤x≤1.
The present invention further provides the AxBO2(kernel)-AxMO2(shell), (0.6≤x≤2) layered oxide anode
The preparation method of material, include the following steps: (1) transition metal salt is configured in proportion total concentration of metal ions be 1.5~
The solution 1 and solution 2 of 3mol/L, the solution 1 are transition metal salt solution corresponding to high electrochemical component, and the solution 2 is
Metallic solution corresponding to the good component of air stability；(2) compound concentration is the aqueous slkali of 3~5mol/L；(3) compound concentration is
The enveloping agent solution of 3~5mol/L；(4) coprecipitation is used, solution 1,2 is respectively placed in reactive tank 1,2, it will by the pump housing
Solution 2 is added gradually in solution 1 and is stirred, and at the same time, the component solution containing high electrochemical is slowly reduced, air
The component having good stability gradually increases；Step (2) and (3) prepared aqueous slkali and complexing agent are passed through into the pump housing gradually simultaneously
It is added in reactive tank, adjusting reaction temperature is 30~80 DEG C, and solution pH value is 7~12, and stirring rate is 800~1200rpm,
Precipitate the positive stratiform oxide precursor for generating chemical constituent and gradient being presented simultaneously by multielement；(5) by step (4)
Gained presoma is washed, dry, by solid phase method by all metals in lithium, sodium source compound and presoma in molar ratio
The uniform mixed grinding of 0.7~1.2:1, it is high electrochemical component that calcining, which forms kernel, and shell is the good component of air stability
Spheric granules anode stratiform oxide particle.
In above-mentioned preparation method, later period calcination temperature is 500-800 DEG C, preferably 700 DEG C；Calcination time is 20-30h,
It is preferred that for 24 hours, in the temperature-rise period of calcining, heating rate is 2-10 DEG C of min-1, preferably 5 DEG C of min-1。
(5) presoma obtained by step (4) is washed, it is dry, while by compounds such as lithium source, sodium source or potassium resources with before
All metals uniform mixed grinding of 0.7~1.2:1 in molar ratio in body is driven, it is high electrochemical component, shell that calcining, which forms kernel,
For the spheric granules of the good component of air stability, i.e., layered oxide cell positive electrode.
A kind of compound comprising positive electrode of the present invention, containing the positive electrode and conductive additive,
Binder and coordinative solvent, the conductive additive are one of carbon black, Super-P, Ketjen black or a variety of, it is therefore preferable to
Super P；The binder is Kynoar (PVDF), polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), butylbenzene rubber
One of glue/sodium carboxymethylcellulose, sodium alginate (SA), gelatin are a variety of, preferably Kynoar (PVDF).
The synthetic method of above-mentioned compound: the positive electrode and conductive additive, binder and solvent are mixed
Afterwards, it is made through slurrying, smear, drying；Preferably, the positive electrode content is 80wt%, conductive additive Super P content
For 10wt%, binder PVDF content is 10wt%.
It is a kind of with compound of the present invention be anode alkali metal-ion battery, by anode, diaphragm, organic electrolysis
The lithium metal of liquid and cathode, sodium or potassium composition, the organic electrolyte be carbonic ester electrolyte, concentration 0.1-2M, preferably
1M；In the carbonic ester electrolyte, solvent is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and carbon
The mixed solvent of at least one of acid propylene ester, preferably ethylene carbonate and propene carbonate；Solute is selected from hexafluorophosphoric acid
One of lithium, sodium hexafluoro phosphate or sodium chloride.
The preparation method of the excellent layered oxide positive electrode of one kind air stability provided by the invention, advantage are
Preparation process can control the kernel of product grain by regulating and controlling the ingredient proportion of metal oxide to the ratio of phase each between surface layer,
The layered oxide positive electrode air stability being prepared is good.Such stratiform transition metal oxide as alkali metal from
Excellent electrochemical stability is shown when sub- cell positive material, and this kind of material can be directly as alkali metal-ion battery
Electrode material use.By forming the good component of air stability in particle surface, propose material air stability
It rises, material volume energy density improves, and each active material gives full play to electro-chemical activity, and then optimizes alkali metal-ion battery
Chemical property.
Compared with prior art, the present invention is by forming good group of air stability in particle surface during the preparation process
Point, successfully synthesizing kernel is high electrochemical component, and shell is the spheric granules A of the good component of air stabilityxBO2(kernel)-
AxMO2(shell) alkali metal-ion battery anode layered oxide material.
Detailed description of the invention
Fig. 1 is Na0.67Mn0.7Ni0.2Mg0.1O2It is formed in preparation process inside particle to chemical constituent gradient between surface layer
Layered oxide positive electrode scanning electron microscope sem, (a) Na0.67Mn0.7Ni0.2Mg0.1O2Shape appearance figure；(b) it is
Na0.67Mn0.7Ni0.2Mg0.1O2Particle sectional view.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Reagent described in following embodiments and instrument commercially obtain unless otherwise specified.
Embodiment 1
(1) it prepares inside particle to the layered oxide positive electrode of chemical constituent gradient between surface layer
Na0.67Mn0.7Ni0.2Mg0.1O2.Wherein internal composition is Na0.67Mn0.8Mg0.2O2High electrochemical component, shell is
Na0.67Ni0.33Mn0.67O2The good component of air stability.
NiSO is weighed in proportion4·6H2O、MnSO4·H2O、MgSO4·7(H2O)、NH4OH, NaOH, preparing metal ion
The complexing agent 4 that the aqueous slkali 3 and concentration that the solution 1 and 2 and concentration that concentration is 2mol/L are 4mol/L are 4mol/L, wherein molten
Mn:Mg=0.80:0.20 in liquid 1, solution 1,2 is respectively placed in by Ni:Mn=0.33:0.67 using coprecipitation in solution 2
In reactive tank 1,2, solution 2 is added gradually in solution 1 and is stirred by the pump housing, at the same time, contains high electrochemical
Component slowly reduce with the dropwise addition of solution 2, the good component of air stability gradually increases；Simultaneously by prepared alkali soluble
Liquid and complexing agent are added gradually in reactive tank by the pump housing, and adjusting reaction temperature is 30~80 DEG C, and solution pH value is 10~12,
Stirring rate is 800~1200rpm, precipitates the positive stratiform oxygen for generating chemical constituent and gradient being presented simultaneously by multielement
Compound presoma.Gained presoma is washed, it is dry, while by all metals in sodium source compound and presoma by mole
Mixed grinding more uniform than 0.7~1.2:1, it is high electrochemical component that calcining, which forms kernel, and shell is the good component of air stability
Spheric granules anode stratiform oxide particle.
(2) it prepares inside particle to the Na of chemical constituent gradient between surface layer0.67Mn0.7Ni0.2Mg0.1O2Compound is just
Pole
In mass ratio by the positive electrode of preparation and conductive additive Super-P, binder polyvinylidene fluoride (PVDF)
It is uniformly mixed for 8: 1: 1, and appropriate N-Methyl pyrrolidone is added, obtaining compound just by techniques such as slurrying, smear, dryings
Pole.
(3) sodium-ion battery is assembled
The compound anode of above-mentioned preparation is assembled into sodium-ion battery with sodium cathode, electrolyte selects carbonic ester electrolyte
(1M NaClO4EC/PC (volume ratio 1:1) solution).
(4) sodium-ion battery is tested
The charge-discharge test under constant multiplying power 0.2C is carried out to above-mentioned sodium-ion battery using charge and discharge instrument.
Embodiment 2
(1) it prepares inside particle to the layered oxide positive electrode of chemical constituent gradient between surface layer
LiNi0.8Co0.15Al0.05O2, wherein it is LiNi inside particle0.9Co0.1O2High electrochemical component, shell is
LiNi0.7Co0.2Al0.1O2The good component of air stability.
NiSO is measured in proportion4·6H2O、CoSO4·7H2O、NH4OH、NaOH、Al2(SO4)3, preparing metal ion concentration
The complexing agent 4 that the aqueous slkali 3 and concentration that solution 1 and 2 and concentration for 2mol/L are 4mol/L are 4mol/L, wherein solution 1
Middle Ni:Co=0.90:0.10, Ni:Co:Al=0.70:0.20:0.10 in solution 2 are distinguished solution 1,2 using coprecipitation
It is placed in reactive tank 1,2, solution 2 is added gradually in solution 1 and is stirred by the pump housing, at the same time, contain high electricity
The component of chemistry is slowly reduced with the dropwise addition of solution 2, and the good component of air stability gradually increases；It simultaneously will be prepared
Aqueous slkali and complexing agent are added gradually in reactive tank by the pump housing, and adjusting reaction temperature is 30~80 DEG C, and solution pH value is 10
~12, stirring rate is 800~1200rpm, precipitates the hydrogen-oxygen for generating chemical constituent and gradient being presented simultaneously by multielement
Compound presoma.Gained presoma is washed, it is dry, while by all metals in Li source compound and presoma by mole
Mixed grinding more uniform than 0.7~1.2:1, it is high electrochemical component that calcining, which forms kernel, and shell is the good component of air stability
Spheric granules anode stratiform oxide particle.
(2) it prepares inside particle to the layered oxide positive electrode of chemical constituent gradient between surface layer
LiNi0.8Co0.15Al0.05O2Compound anode (the specific steps are the same as those in embodiment 1)
(3) lithium ion battery is assembled
The compound anode of above-mentioned preparation is assembled into sodium-ion battery with cathode of lithium, electrolyte selects carbonic ester electrolyte
(1.2M LiPF6EC/EMC (volume ratio 3:7) solution).
(4) lithium ion battery test (the specific steps are the same as those in embodiment 1)
Embodiment 3
(1) it prepares inside particle to the layered oxide positive electrode Na of chemical constituent gradient between surface layer0.67Ni0.1 3Fe0.25Mn0.585Zn0.035O2(raw material NaOH, NiSO4·6H2O、MnSO4·H2O、FeSO4·7(H2O)、ZnSO4·7
(H2O), remaining step is with embodiment 1) wherein, particle kernel is Na2/3Fe1/2Mn1/2O2High electrochemical component, shell is
Na0.66Mn0.67Ni0.26Zn0.07O2The good component of air stability
(2) it prepares inside particle to the Na of chemical constituent gradient between surface layer0.67Ni0.13Fe0.25Mn0.585Zn0.035O2
Compound anode (the specific steps are the same as those in embodiment 1)
(3) assemble sodium-ion battery (the specific steps are the same as those in embodiment 1)
(4) sodium-ion battery test (the specific steps are the same as those in embodiment 1)
Embodiment 4
(1) it prepares inside particle to the layered oxide positive electrode of chemical constituent gradient between surface layer
NaNi0.5Mn0.35Ti0.15O2.(raw material NaOH, NiSO4·6H2O,TiO2,MnSO4·H2O, remaining step is with embodiment 1)
Wherein, particle kernel is NaNi0.5Mn0.5O2High electrochemical component, shell NaNi0.5Mn0.2Ti0.3O2Air stability it is good
Good component.
(2) it prepares inside particle to the NaNi of chemical constituent gradient between surface layer0.5Mn0.2Ti0.3O2Compound anode
(the specific steps are the same as those in embodiment 1)
(3) assemble sodium-ion battery (the specific steps are the same as those in embodiment 1)
(4) sodium-ion battery test (the specific steps are the same as those in embodiment 1)
Embodiment 5
(1) it prepares inside particle to the NaNi of chemical constituent gradient between surface layer0.46Cu0.03Mn0.46Ti0.06Positive material
Material.(raw material NaOH, NiSO4·6H2O、MnSO4·H2O、CuSO4·5H2O、TiO2, remaining step is with embodiment 1) its
In, particle kernel is NaNi0.5Mn0.5O2High electrochemical component, shell NaNi0.45Cu0.05Mn0.4Ti0.1O2Air-stable
The good component of property.
(2) it prepares inside particle to the NaNi of chemical constituent gradient between surface layer0.46Cu0.03Mn0.46Ti0.06Compound
Positive (the specific steps are the same as those in embodiment 1)
(3) assemble sodium-ion battery (the specific steps are the same as those in embodiment 1)
(4) sodium-ion battery test (the specific steps are the same as those in embodiment 1)
Comparative example 1
(1) it prepares inside particle to the homogeneous layered oxide anode material Na of component between surface layer0.67Mn0.8Mg0.2O2
NiSO is measured in proportion4·6H2O、MnSO4·H2O、MgSO4·7(H2O)、NH4OH, NaOH, using coprecipitation,
The uniform hydroxide precursor of component is synthesized, gained presoma is washed, it is dry, while by sodium source compound and forerunner
The uniform mixed grinding of 0.7~1.2:1, calcining form intragranular component uniform spherical to all metal ions in molar ratio in body
The positive stratiform oxide particle of grain.
(2) it prepares inside particle to the uniform Na of component between surface layer0.67Mn0.8Mg0.2O2(specific steps are same for compound anode
Embodiment 1)
(3) assemble sodium-ion battery (the specific steps are the same as those in embodiment 1)
(4) sodium-ion battery test (the specific steps are the same as those in embodiment 1)
Comparative example 2
(1) it prepares inside particle to the uniform layered oxide positive electrode LiNi of component between surface layer0.9Co0.1O2
NiSO is measured in proportion4·6H2O、CoSO4·7H2O、NH4It is uniform to synthesize component using coprecipitation by OH, NaOH
Hydroxide precursor, gained presoma is washed, it is dry, while by all metals in Li source compound and presoma
The uniform mixed grinding of 0.7~1.2:1, calcining form the uniform spheric granules anode stratiform oxygen of intragranular component to ion in molar ratio
Compound particle.
(2) it prepares inside particle to the uniform LiNi of component between surface layer0.9Co0.1O2(specific steps are the same as real for compound anode
Apply example 2)
(3) assemble lithium ion battery (specific steps are with embodiment 2)
(4) lithium ion battery test (specific steps are with embodiment 2)
Comparative example 3
(1) it prepares inside particle to the uniform layered oxide positive electrode NaNi of component between surface layer0.5Mn0.5O2.It is (former
Material is NaOH, NiSO4·6H2O,MnSO4·H2O, remaining step is with comparative example 1)
(2) it prepares inside particle to the uniform NaNi of component between surface layer0.5Mn0.5O2(specific steps are the same as real for compound anode
Apply example 1)
(3) assemble sodium-ion battery (the specific steps are the same as those in embodiment 1)
(4) sodium-ion battery test (the specific steps are the same as those in embodiment 1)
Comparative example 4
(1) it prepares inside particle to the uniform layered oxide positive electrode Na of component between surface layer2/3Fe1/2Mn1/2O2。
(raw material NaOH, FeSO4·7H2O,MnSO4·H2O, remaining step is with comparative example 1)
(2) it prepares inside particle to the uniform NaNi of component between surface layer0.5Mn0.5O2(specific steps are the same as real for compound anode
Apply example 1)
(3) assemble sodium-ion battery (the specific steps are the same as those in embodiment 1)
(4) sodium-ion battery test (the specific steps are the same as those in embodiment 1)
The battery charging and discharging test result of 1 embodiment and comparative example of table
It is can be seen that with comparative example through the foregoing embodiment by coprecipitation in the present invention, synthesis has chondritic
Particulate alkali metal ion battery anode layered oxide, by regulating and controlling the ratio of particle kernel to chemical constituents different between shell,
Wherein kernel is high electrochemical component, and shell is the good component of air stability, and then obtains electrochemistry and air stability all
Excellent electrode material.From embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, embodiment 3 and comparative example 4, embodiment 4,5 with
Comparative example 3 it was found that, through the invention in mention the ratio of regulation particle kernel to chemical constituents different between shell, can
The apparent air stability for improving layered cathode oxide, and keep good chemical property；
In conclusion alkali metal-ion battery anode stratified material of the invention has preferable air stability, master
Wanting component part is AxBO2(kernel)-AxMO2(shell) (0.6≤x≤2)；Corresponding compound anode structure stability is stronger,
Thus the present invention is expected to novel prepare the regulatable alkali metal-ion battery anode layer of particle internal chemical component as a kind of
Shape MATERIALS METHODS, has a good application prospect.
Above content is merely a preferred embodiment of the present invention, and is not intended to limit embodiment of the present invention, and this field is general
Logical technical staff's central scope according to the present invention and spirit can very easily carry out corresponding flexible or modification, therefore
Protection scope of the present invention should be subject to protection scope required by claims.
Claims (10)
1. the excellent layered oxide cell positive material of air stability, it is characterised in that: the positive electrode is stratiform oxygen
Compound AxBO2-AxMO2, wherein AxBO2For kernel, kernel is high electrochemical component, AxMO2For shell, shell is air stability
Good component, the A are alkali metal, and the B is the transition metal with electro-chemical activity, and the M is that air stability is excellent
Element, wherein 0.6≤x≤2.
2. the excellent layered oxide cell positive material of air stability according to claim 1, it is characterised in that: institute
It stating A and is selected from one of Li, Na, K, the B is selected from least one of Fe, Co, Ni, Mn, V, Cr, and the M is selected from Cu, Li,
At least one of Mg, Ca, Ba.
3. the excellent layered oxide cell positive material of air stability according to claim 1, it is characterised in that:
0.67≤x≤1。
4. the synthetic method of the excellent layered oxide cell positive material of air stability as described in claim 1, special
Sign is: it includes the following steps:
(1) transition metal salt is configured to the solution 1 and solution 2 that total concentration of metal ions is 1.5 ~ 3mol/L in proportion, it is described
Solution 1 is transition metal salt solution corresponding to high electrochemical component, and the solution 2 is gold corresponding to the good component of air stability
Belong to solution；
(2) compound concentration is the aqueous slkali of 3 ~ 5mol/L；
(3) compound concentration is the enveloping agent solution of 3 ~ 5mol/L；
(4) coprecipitation is used, solution 1,2 is respectively placed in reactive tank 1,2, is added gradually to solution 2 by the pump housing molten
It in liquid 1 and is stirred, at the same time, the component solution containing high electrochemical is slowly reduced, the good component of air stability
It gradually increases；Step (2) and (3) prepared aqueous slkali and enveloping agent solution are added gradually to reactive tank by the pump housing simultaneously
In, adjusting reaction temperature is 30 ~ 80 DEG C, and solution pH value is 7 ~ 12, and stirring rate is 800 ~ 1200rpm, simultaneously by multielement
Precipitating generates the positive stratiform oxide precursor that gradient is presented in chemical constituent；
(5) presoma obtained by step (4) is washed, it is dry, while will be in lithium source, sodium source or potassium resource compound and presoma
The uniform mixed grinding of 0.7 ~ 1.2:1, calcining form kernel as high electrochemical component to all metals in molar ratio, and shell is that air is steady
The spheric granules of qualitative good component, i.e., layered oxide cell positive electrode.
5. the synthetic method of the excellent layered oxide cell positive material of air stability according to claim 4,
Be characterized in that: the calcination temperature of step (4) is 500-800 DEG C, calcination time 20-30h, in the temperature-rise period of calcining, heating
Rate is 2-10 DEG C of min-1。
6. a kind of compound comprising positive electrode described in claim 1, it is characterised in that: in the compound containing it is described just
Pole material and conductive additive, binder and coordinative solvent, the conductive additive are carbon black, in Super-P, Ketjen black
It is one or more；The binder is Kynoar, polyacrylic acid, sodium carboxymethylcellulose, butadiene-styrene rubber/carboxymethyl fibre
Tie up one of plain sodium, sodium alginate, gelatin or a variety of.
7. a kind of synthetic method of compound as claimed in claim 6, it is characterised in that: by the positive electrode, and lead
After electric additive, binder and solvent mix, it is made through slurrying, smear, drying.
8. it is a kind of with compound as claimed in claim 6 be anode alkali metal-ion battery, it is characterised in that: its by anode,
Diaphragm, the lithium metal of organic electrolyte and cathode, sodium or potassium composition, the organic electrolyte are carbonic ester electrolyte, and concentration is
0.1-2 M；In the carbonic ester electrolyte, solvent is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate
At least one of ester and propene carbonate, solute are selected from one of lithium hexafluoro phosphate, sodium hexafluoro phosphate or sodium chloride.
9. a kind of method for improving metal ion cell positive material air stability, it is characterised in that: pass through coprecipitation, benefit
With different metal doped alkali metal ion battery anode layered oxide, the layered oxide battery with chondritic is being synthesized just
Pole materials AxBO2-AxMO2, 0.6≤x≤2, including core AxBO2With shell AxMO2, wherein kernel is high electrochemical component, shell
For the good component of air stability, the A is alkali metal, and the B is the transition metal with electro-chemical activity, and the M is sky
The element of gas excellent in stability.
10. the method according to claim 9 for improving metal ion cell positive material air stability, feature exist
In: the A is selected from one of Li, Na, K, and the B is selected from least one of Fe, Co, Ni, Mn, V, Cr, and the M is selected from
At least one of Cu, Li, Mg, Ca, Ba.
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| CN114715953A (en) * | 2022-03-14 | 2022-07-08 | 中国科学技术大学 | Method for preparing Cu and Zn doped layered oxide sodium ion battery anode material with assistance of precursor and application of method |
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| CN106673075A (en) * | 2017-01-03 | 2017-05-17 | 中国科学院化学研究所 | Modified O3 type layered cathode material of sodium-ion battery, and preparation method and application thereof |
| CN109449418A (en) * | 2018-11-05 | 2019-03-08 | 中南大学 | Compound sodium ion positive electrode with core-shell structure and preparation method thereof |
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