CN114975958A - Negative electrode material for sodium ion battery, preparation method of negative electrode material, negative plate and sodium ion battery - Google Patents
Negative electrode material for sodium ion battery, preparation method of negative electrode material, negative plate and sodium ion battery Download PDFInfo
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- CN114975958A CN114975958A CN202210711332.5A CN202210711332A CN114975958A CN 114975958 A CN114975958 A CN 114975958A CN 202210711332 A CN202210711332 A CN 202210711332A CN 114975958 A CN114975958 A CN 114975958A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 95
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 47
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 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 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 238000005056 compaction Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 abstract description 13
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 24
- 239000011777 magnesium Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Organic Chemistry (AREA)
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- Composite Materials (AREA)
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- Secondary Cells (AREA)
Abstract
The invention provides a negative electrode material for a sodium ion battery, a preparation method of the negative electrode material, a negative electrode sheet and the sodium ion battery, wherein the molecular structural formula of the negative electrode material is P 2‑a Na a Ti x M 3‑x O 7‑y H y The tap density of the negative electrode material is 0.8-2.5 g/cm 3 Pressing at 10 tons pressureThe solid density is 2.0-4 g/cm 3 . By adopting the cathode material with the specific composition and controlling the tap density and the compacted density of the cathode material within the ranges, the conductivity of the cathode material can be effectively improved, and simultaneously, the capacity performance of the cathode material and the structural stability of the cathode material in the charging and discharging processes are effectively improved. Therefore, the problems of low conductivity and poor cycle stability of the conventional negative electrode material sodium titanate are solved.
Description
Technical Field
The invention relates to the field of sodium batteries, in particular to a negative electrode material for a sodium ion battery, a preparation method of the negative electrode material, a negative plate and the sodium ion battery.
Background
With the gradual application of large-scale energy storage and electric automobiles, the demand of lithium ion batteries is increasing day by day, and the supply problem of metal lithium resources is embarrassing day by day. Sodium resources in the earth crust are abundant, low in price and widely distributed, and sodium ion batteries developed based on sodium elements are greatly concerned by research and development personnel in recent years. The excellent electrochemical performance of the sodium ion battery can well meet the application requirements of power storage, particularly large-scale energy storage.
The negative electrode material for the sodium ion battery of practical use at present is hard carbon material, but hard carbon material has that the cycle performance is unsatisfactory, and sodium metal is easily appeared on hard carbon surface in the charging process, impales the diaphragm easily and leads to positive negative pole short circuit, causes the shortcoming of battery explosion on fire. The sodium titanate has small volume expansion effect before and after sodium intercalation/deintercalation, stable structure and good safety, and is suitable for being used as a negative electrode active material of a sodium ion battery. However, the conventional sodium titanate has the disadvantages of poor conductivity, low first-time efficiency, insufficient capacity exertion and unsatisfactory cycle performance.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the negative electrode material for the sodium ion battery is provided to solve the problems of low conductivity and poor cycle stability of the sodium titanate of the current negative electrode material for the sodium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a negative electrode material for sodium ion battery has molecular structure formula P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is at least one of Li, K, Rb, Cs, Zn, Mg and Ca; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ 、Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is at least one of F-, Cl-, Br-and I-; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1; the tap density of the negative electrode material is 0.8-2.5 g/cm 3 The compaction density is 2.0-4 g/cm under the pressure of 10 tons 3 。
Preferably, the molecular structural formula of the negative electrode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is Rb and/or Cs; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ 、Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F-Cl ﹣ 、Br ﹣ And I ﹣ At least one of (a); a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1.
Preferably, the molecular structural formula of the negative electrode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is at least one of Li, K, Rb, Cs, Zn, Mg and Ca; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ And is Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ 、Br ﹣ And I < - >; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1.
Preferably, the molecular structural formula of the negative electrode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is Rb and/or Cs; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ And is Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4 + 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ 、Br ﹣ And I < - >; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1.
Preferably, the particle size D50 of the negative electrode material is 1-20 μm; the specific surface area of the negative electrode material is 0.3-10 m 2 /g。
Another object of the present invention is to provide a method for preparing the negative electrode material for sodium ion battery, comprising the steps of:
s1, premixing a stoichiometric P source compound, a stoichiometric sodium source compound, a stoichiometric titanium source compound, a stoichiometric M source compound and a stoichiometric H source compound to obtain premixed powder;
s2, mixing the premixed powder obtained in the step S1 with water and ammonium polyacrylate, and performing ball milling to obtain slurry, wherein the primary particle size of the slurry ranges from 100 nm to 800 nm;
s3, spray drying the slurry obtained in the step S2, granulating to obtain a precursor, sintering the precursor, and cooling to obtain a powder with the sub-formula P 2-a Na a Ti x M 3-x O 7-y H y The negative electrode material of (1).
Preferably, the particle size of the titanium source compound is 100-600 nm; the mass of the premixed powder and water is 1: (4-8); the mass of the ammonium polyacrylate is 1-5% of the mass of the water.
Preferably, in the step S3, a spray dryer is adopted for spray drying, wherein the inlet temperature of the spray dryer is 200-300 ℃, and the outlet temperature of the spray dryer is 100-150 ℃; the sintering temperature is 750-850 ℃, and the sintering time is 18-30 h.
Another object of the present invention is to provide a negative electrode sheet comprising the negative electrode material for sodium-ion batteries as defined in any one of the above.
The invention also provides a sodium ion battery, which comprises a positive plate, a negative plate and a diaphragm arranged between the positive plate and the negative plate, wherein the negative plate is the negative plate.
Compared with the prior art, the invention has the beneficial effects that: the negative electrode material for the sodium ion battery provided by the invention adopts the negative electrode material with the specific composition, and the tap density and the compaction density of the negative electrode material are controlled within the range, so that the conductivity of the negative electrode material can be effectively improved, and the capacity performance of the negative electrode material and the structural stability of the negative electrode material in the charging and discharging processes are effectively improved. Therefore, the problems of low conductivity and poor cycle stability of the conventional negative electrode material sodium titanate are solved.
Detailed Description
1. Negative electrode material for sodium ion battery
The invention aims to provide a negative electrode material for a sodium ion battery, wherein the molecular structural formula of the negative electrode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is at least one of Li, K, Rb, Cs, Zn, Mg and Ca; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ 、Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ At least one of Br-and I-; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1; the tap density of the negative electrode material is 0.8-2.5 g/cm 3 The compaction density is 2.0-4 g/cm under the pressure of 10 tons 3 。
The negative electrode material for the sodium ion battery provided by the invention adopts the negative electrode material with the specific composition, and controls the tap density and the compaction density within the range, so that the conductivity of the negative electrode material can be effectively improved, and simultaneously, the capacity performance of the negative electrode material and the structural stability of the negative electrode material in the charging and discharging processes are effectively improved. Among them, the present inventors have found that when the Na site is partially substituted, the insertion/extraction of sodium ions is more facilitated, and the power density of the material is further improved. In addition, when the Ti site is partially replaced by other transition metal ions, the crystal structure of the obtained sodium titanate material has better ordering, and the first coulombic efficiency of the cathode material can be effectively improved.
Wherein the tap density of the cathode material can be 0.8-2.5 g/cm 3 Specifically 0.8 to 1.0g/cm 3 、1.0～1.2g/cm 3 、1.2～1.4g/cm 3 、1.4～1.6g/cm 3 、1.6～1.8g/cm 3 、1.8～2.0g/cm 3 、2.0～2.2g/cm 3 Or 2.2 to 2.5g/cm 3 . The compacted density of the negative electrode material under the pressure of 10 tons is 2.0-4 g/cm 3 Specifically, it may be 2.0 to 2.2g/cm 3 、2.2～2.4g/cm 3 、2.4～2.6g/cm 3 、2.6～2.8g/cm 3 、2.8～3.0g/cm 3 、3.0～3.2g/cm 3 、3.2～3.4g/cm 3 、3.4～3.6g/cm 3 、3.6～3.8g/cm 3 Or 3.8 to 4.0g/cm 3 。
In some embodiments, the molecular structure of the anode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is Rb and/or Cs; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ 、Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F-, Cl-, Br-or I ﹣ At least one of; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1. The part with the Na position substituted preferably adopts ions with larger ionic radius than Na, namely P is preferably Rb and/or Cs, and the process of the intercalation/deintercalation of sodium ions is easier, thus being more beneficial to improving the power density of the material.
In some embodiments, the molecular structure of the anode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is at least one of Li, K, Rb, Cs, Zn, Mg and Ca; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ And is Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ 、Br ﹣ And I ﹣ At least one of; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1. Partial substitution of Ti site with a part substituted with a lower cation, preferably Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ The inventor finds that the ion diffusion coefficient of the doped and substituted sodium titanate is obviously improved due to the introduction of low-valence ions, defect sites and cavities in the crystal are increased, the migration and diffusion of sodium ions in the crystal are facilitated, and the good cycle performance can be realized while the capacity of the sodium titanate can be stably exerted. Meanwhile, the other part of the Ti position is replaced by high-valence cations, so that the matching performance of the Ti position and low-valence ions is better, and the electrochemical performance of the cathode material is improved to be more excellent.
In some embodiments, the molecular structure of the anode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is Rb and/or Cs; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ And is Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3 + 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ 、Br ﹣ And I ﹣ At least one of; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1. The inventor also finds that the Na-substituted part preferably adopts ions with larger ionic radius than Na, namely P is preferably Rb and/or Cs, and synchronously matches with low-valence cationsPartial substitution of Ti, P negative electrode material composed of both 2-a Na a Ti x M 3-x O 7-y H y The conductivity of the cathode material can be better improved, the structural stability of the cathode material in the charging and discharging process is effectively improved, and the capacity performance of the cathode material is improved.
In some embodiments, the particle size D50 of the negative electrode material is 1-20 μm; specifically, the particle diameter is 1 to 2 μm, 2 to 4 μm, 4 to 6 μm, 6 to 8 μm, 8 to 10 μm, 10 to 12 μm, 12 to 14 μm, 14 to 16 μm, 16 to 18 μm or 18 to 20 μm. The tap density and the compacted density are designed by utilizing the particle size, so that the tap density and the compacted density can be better ensured to be in the ranges, and meanwhile, the particle size has better porosity, and is more favorable for the intercalation/deintercalation of sodium ions.
In some embodiments, the specific surface area of the negative electrode material is 0.3-10 m 2 (ii)/g; specifically, the thickness can be 0.3 to 1m 2 /g、1～2m 2 /g、2～3m 2 /g、3～4m 2 /g、4～5m 2 /g、5～6m 2 /g、6～7m 2 /g、7～8m 2 /g、8～9m 2 (ii)/g or 9 to 10m 2 (ii) in terms of/g. Maintaining the specific surface area, the anode material P 2-a Na a Ti x M 3-x O 7-y H y The negative electrode material is applied to a negative electrode plate and a sodium ion battery, has better liquid absorption capacity, is matched with the compaction density and the tap density, and can effectively improve the first coulomb efficiency and the cycle capacity retention rate of the negative electrode after being applied to the sodium ion battery.
The second aspect of the present invention is directed to a method for preparing the anode material, comprising the steps of:
s1, premixing a stoichiometric P source compound, a stoichiometric sodium source compound, a stoichiometric titanium source compound, a stoichiometric M source compound and a stoichiometric H source compound to obtain premixed powder;
s2, mixing the premixed powder obtained in the step S1 with water and ammonium polyacrylate, and performing ball milling to obtain slurry, wherein the primary particle size of the slurry ranges from 100 nm to 800 nm;
s3, spray drying the slurry obtained in the step S2, granulating to obtain a precursor, and then carrying out spray drying on the precursorSintering the body, cooling to obtain a powder with the formula P 2-a Na a Ti x M 3-x O 7-y H y The negative electrode material of (1).
In some embodiments, the titanium source compound has a particle size of 100 to 600 nm; the mass of the premixed powder and water is 1: (4-8); the mass of the ammonium polyacrylate is 1-5% of the mass of the water.
In some embodiments, in step S3, spray drying is performed by using a spray dryer, wherein the inlet temperature of the spray dryer is 200 to 300 ℃ and the outlet temperature of the spray dryer is 100 to 150 ℃; the sintering temperature is 750-850 ℃, and the sintering time is 18-30 h. Preferably, the inlet temperature of the spray dryer is 250 ℃ and the outlet temperature is 120 ℃; the sintering temperature is 800 ℃, and the sintering time is 24 h.
P is prepared by the preparation method 2-a Na a Ti x M 3-x O 7-y H y The cathode material has a better crystal structure, higher conductivity, and better material stability and cycle performance.
2. Negative plate
The third aspect of the invention is directed to a negative electrode sheet comprising the negative electrode material for sodium-ion batteries as defined in any one of the above.
3. Sodium ion battery
The invention aims at providing a sodium-ion battery, which comprises a positive plate, a negative plate and a diaphragm arranged between the positive plate and the negative plate, wherein the negative plate is the negative plate.
Preferably, the positive electrode active material adopted by the positive electrode plate is Na a Fe 1-x-y-z-v Ni x Mn y Ti z Zr v O 2-b F b Wherein a, x, y, z, v and b are mole fractions, a is more than or equal to 0.5 and less than or equal to 1.0, x is more than or equal to 0.2 and less than or equal to 0.7, y is more than or equal to 0.2 and less than or equal to 0.7, z is more than or equal to 0.01 and less than or equal to 0.3, v is more than or equal to 0.01 and less than or equal to 0.3, and b is more than or equal to 0.01 and less than or equal to 0.2.
The preparation method of the anode active material comprises the following steps:
s1, weighing a sodium source compound, an iron source compound, a nickel source compound, a manganese source compound, a titanium source compound, a zirconium source compound and a fluorine source compound according to a stoichiometric formula, and premixing to obtain premixed powder;
s2, adding the premixed powder, the solvent and the dispersing agent into a nano sand mill for ball milling to obtain slurry, wherein the primary particle size of the slurry ranges from 100 nm to 200 nm;
s3, carrying out spray drying granulation on the slurry to obtain a precursor; then sintering and cooling the precursor to obtain Na a Fe 1-x-y-z-v Ni x Mn y Ti z Zr v O 2-b F b The layered oxide positive electrode active material of (1).
The positive active material is matched with the negative material for use, so that the sodium ion battery has better stability and cycle performance.
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantageous effects will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
A negative electrode material for sodium ion battery has a molecular structural formula of Rb 0.1 Na 1.9 Ti 2 Mg 0.5 Sn 0.5 O 6.5 F 0.5 The tap density of the negative electrode material is 1.8g/cm 3 And a compacted density of 3g/cm at a pressure of 10 tons 3 (ii) a The particle size D50 is 5 μm; specific surface area of 3m 2 /g。
The preparation method of the anode material comprises the following steps:
s1, weighing rubidium carbonate, sodium carbonate, 300nm titanium dioxide, tin oxide, magnesium carbonate and ammonium fluoride according to a stoichiometric formula, grinding and premixing to obtain premixed powder; wherein Rb: na: ti: mg: sn: the F molar ratio is 0.1: 1.9: 2: 0.5: 0.5: 0.5;
s2, mixing the premixed powder with deionized water according to the mass ratio of 1: 5, adding ammonium polyacrylate (2% of the mass of deionized water) into a nano sand mill, and performing high-energy ball milling for 15 hours to obtain slurry, wherein the primary particle size of the slurry is about 200 nm;
s3, spray drying and granulating the slurry to obtain a precursor, wherein the inlet temperature of a spray dryer is 250 ℃, and the outlet temperature of the spray dryer is 120 ℃; sintering the precursor powder for 24h at 800 ℃ in air atmosphere, and naturally cooling to room temperature to obtain the precursor powder with the molecular formula of Rb 0.1 Na 1.9 Ti 2 Mg 0.5 Sn 0.5 O 6.5 F 0.5 The sodium titanate negative electrode material for a sodium ion battery.
Example 2
Different from the embodiment 1, the negative electrode material of the embodiment has the molecular formula of Rb 0.1 Na 1.9 Ti 2.5 Mg 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 3
Different from the embodiment 1, the negative electrode material of the embodiment has the molecular formula of Rb 0.1 Na 1.9 Ti 2.5 Sn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 4
Unlike example 1, the negative electrode material of this example, whose molecular formula is Li, was provided 0.1 Na 1.9 Ti 2.5 Mg 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 5
Unlike example 1, the negative electrode material of this example, whose molecular formula is Li, was provided 0.1 Na 1.9 Ti 2.5 Sn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 6
Unlike example 1, the negative electrode material of this example, whose molecular formula is Li, was provided 0.1 Na 1.9 Ti 2 Mg 0.5 Sn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 7
Different from the embodiment 1, the negative electrode material of the embodiment has the molecular formula of Rb 0.1 Na 1.9 Ti 2.5 Mn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 8
Different from the embodiment 1, the negative electrode material of the embodiment has the molecular formula of Rb 0.1 Na 1.9 Ti 2 Mn 0.5 Sn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 9
Unlike example 1, the negative electrode material of this example, whose molecular formula is Li, was provided 0.1 Na 1.9 Ti 2.5 Mn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 10
Unlike example 1, the negative electrode material of this example, whose molecular formula is Li, was provided 0.1 Na 1.9 Ti 2 Mn 0.5 Sn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 11
Different from the embodiment 1, the negative electrode material of the embodiment has the molecular formula of Rb 0.5 Na 1.5 Ti 2 Mg 0.5 Sn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 12
Different from example 1 in the negative electrode materialIn this embodiment, the molecular formula of the negative electrode material is Rb 0.8 Na 1.2 Ti 2 Mg 0.5 Sn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 13
Different from the embodiment 1, the negative electrode material of the embodiment has the molecular formula of Rb 0.1 Na 1.9 Ti 2.5 Mg 0.4 Sn 0.1 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 14
Different from the embodiment 1, the negative electrode material of the embodiment has the molecular formula of Rb 0.1 Na 1.9 Ti 1.5 Mg 1.0 Sn 0.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 15
Different from the embodiment 1, the negative electrode material of the embodiment has the molecular formula of Rb 0.1 Na 1.9 Ti 1.5 Mg 1.5 O 6.5 F 0.5 。
See example 1 for the rest, which is not described here.
Example 16
Unlike example 1, the tap density of the negative electrode material of this example was 0.8g/cm 3 The compacted density at 10 tons of pressure is 2g/cm 3 。
See example 1 for the rest, which is not described here.
Example 17
Unlike example 1, the tap density of the negative electrode material of this example was 2.0g/cm 3 And a compacted density of 3.5g/cm at a pressure of 10 tons 3 。
See example 1 for the rest, which is not described here.
Example 18
Unlike example 1Similarly, the tap density of the negative electrode material of this example was 2.5g/cm 3 And a compacted density of 4g/cm at a pressure of 10 tons 3 。
See example 1 for the rest, which is not described here.
The negative electrode material obtained in the above examples 1 to 18 was applied to a negative electrode sheet, and 1.9g of the obtained negative electrode material was weighed, 0.05g of carbon black and 0.05g of polyvinylidene fluoride dissolved in N, N' -methylpyrrolidone were added, and the mixture was homogenized and coated on a copper foil to prepare a negative electrode sheet.
The obtained negative plate is applied to a button cell, and the performance of the button cell is tested.
Button cell: in a glove box in argon atmosphere, metal sodium is used as a counter electrode, glass fiber is used as a diaphragm, and 1M/NaPF 6 And PC: EMC: EC (volume ratio 1: 1: 1) is used as electrolyte, and a 2032 coin cell is assembled.
And (3) performance testing: charging the button cell to 4.25V at a constant current of 1C at 25 +/-2 ℃, then charging to 0.05C at a constant voltage of 4.25V, standing for 5min, and then discharging to 2.8V at a constant current of 1C, wherein the process is a charging and discharging cycle process, the discharge capacity at this time is the discharge capacity of the first cycle, and the first coulombic efficiency of the button cell is calculated. And then, continuously carrying out 100-time cyclic charge and discharge tests on the button cell according to the method, recording the discharge capacity of each cycle, and calculating the cycle capacity retention rate of the 100 th circle.
The test results are shown in table 1 below.
TABLE 1
| Discharge capacity (mAh/g) | First coulombic efficiency (%) | Capacity of 100 turnsRetention ratio (%) | |
| Example 1 | 115 | 81％ | 95％ |
| Example 2 | 110 | 77％ | 90％ |
| Example 3 | 104 | 73％ | 85％ |
| Example 4 | 105 | 74％ | 88％ |
| Example 5 | 101 | 71％ | 81％ |
| Example 6 | 111 | 78％ | 91％ |
| Example 7 | 108 | 76％ | 90％ |
| Practice ofExample 8 | 114 | 80％ | 94％ |
| Example 9 | 102 | 72％ | 84％ |
| Example 10 | 109 | 77％ | 90％ |
| Example 11 | 109 | 76％ | 83％ |
| Example 12 | 95 | 67％ | 78％ |
| Example 13 | 110 | 76％ | 91％ |
| Example 14 | 101 | 73％ | 79％ |
| Example 15 | 98 | 71％ | 75％ |
| Example 16 | 106 | 75％ | 87％ |
| Example 17 | 105 | 74％ | 85％ |
| Example 18 | 101 | 71％ | 81％ |
As can be seen from comparison among the test results of the above examples 1 to 18, the negative electrode material provided by the invention has good discharge capacity, first coulombic efficiency and cycle retention rate when applied to a sodium ion battery, and effectively solves the problems of low conductivity, poor cycle stability and low safety performance of sodium titanate as the negative electrode material of the sodium ion battery.
Among them, it can be found from the comparison of examples 1 to 15 that when ions with larger ionic radius such as Rb are partially substituted by Na sites, the obtained negative electrode material has better first coulombic efficiency and cycle performance than when ions with smaller ionic radius such as Li are used. In addition, matching partial substitution of low-valence cations for Ti sites can further improve the first coulombic efficiency and the cycle performance; meanwhile, the other Ti position is replaced by high-valence cations, namely, the electrochemical performance of the cathode material is more excellent on the premise of matching use of low price and high price.
In conclusion, the negative electrode material for the sodium ion battery provided by the invention adopts the negative electrode material with the specific composition, so that the conductivity of the negative electrode material can be effectively improved, and simultaneously, the capacity performance and the structural stability of the negative electrode material in the charging and discharging processes are effectively improved, so that the negative electrode material shows excellent electrochemical performance.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The negative electrode material for the sodium-ion battery is characterized in that the molecular structural formula of the negative electrode material is P 2-a Na a Ti x M 3- x O 7-y H y Wherein, P is at least one of Li, K, Rb, Cs, Zn, Mg and Ca; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2 + 、Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ 、Br ﹣ And I ﹣ At least one of; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1; the tap density of the negative electrode material is 0.8-2.5 g/cm 3 The compaction density under 10 tons of pressure is 2.0-4 g/cm 3 。
2. The negative electrode material for sodium-ion battery as claimed in claim 1, wherein the molecular structural formula of the negative electrode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is Rb and/or Cs; mIs Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ 、Mn 3 + 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ 、Br ﹣ And I ﹣ At least one of; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1.
3. The negative electrode material for sodium-ion battery as claimed in claim 1, wherein the molecular structural formula of the negative electrode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is at least one of Li, K, Rb, Cs, Zn, Mg and Ca; m is Li + 、Ni 2+ 、Mg 2 + 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ And is Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ 、Br ﹣ And I ﹣ At least one of (a); a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1.
4. The negative electrode material for the sodium-ion battery according to claim 1, wherein the molecular structural formula of the negative electrode material is P 2-a Na a Ti x M 3-x O 7-y H y Wherein, P is Rb and/or Cs; m is Li + 、Ni 2+ 、Mg 2+ 、Mn 2+ 、Zn 2+ 、Co 2+ 、Ca 2+ And is Mn 3+ 、Al 3+ 、B 3+ 、Cr 3+ 、V 3+ 、Zr 4+ 、Sn 4+ 、V 4+ 、Mo 4+ 、Mo 5+ 、Ru 4+ 、Nb 5+ 、Mo 6+ At least one of; h is F ﹣ 、Cl ﹣ 、Br ﹣ And I ﹣ At least one of; a is more than or equal to 1.5 and less than 2, x is more than or equal to 2 and less than 3, and y is more than or equal to 0.05 and less than 1.
5. The negative electrode material for sodium-ion batteries according to any one of claims 1 to 4, wherein the particle diameter D50 of the negative electrode material is 1 to 20 μm; the specific surface area of the negative electrode material is 0.3-10 m 2 /g。
6. A preparation method of the negative electrode material for the sodium-ion battery as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
s1, premixing a stoichiometric P source compound, a stoichiometric sodium source compound, a stoichiometric titanium source compound, a stoichiometric M source compound and a stoichiometric H source compound to obtain premixed powder;
s2, mixing the premixed powder obtained in the step S1 with water and ammonium polyacrylate, and performing ball milling to obtain slurry, wherein the primary particle size of the slurry ranges from 100 nm to 800 nm;
s3, spray drying the slurry obtained in the step S2, granulating to obtain a precursor, sintering the precursor, and cooling to obtain a powder with the sub-formula P 2-a Na a Ti x M 3-x O 7-y H y The negative electrode material of (1).
7. The method for preparing the negative electrode material for the sodium-ion battery according to claim 6, wherein the particle size of the titanium source compound is 100 to 600 nm; the mass of the premixed powder and water is 1: (4-8); the mass of the ammonium polyacrylate is 1-5% of the mass of the water.
8. The method for preparing the negative electrode material for the sodium-ion battery according to claim 6, wherein in step S3, a spray dryer is used for spray drying, wherein the inlet temperature of the spray dryer is 200-300 ℃, and the outlet temperature of the spray dryer is 100-150 ℃; the sintering temperature is 750-850 ℃, and the sintering time is 18-30 h.
9. A negative electrode sheet comprising the negative electrode material for sodium-ion batteries according to any one of claims 1 to 5.
10. A sodium ion battery comprising a positive plate, a negative plate and a separator interposed between said positive plate and said negative plate, wherein said negative plate is the negative plate of claim 9.
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