CN114988481B - Sodium ion battery anode material precursor and preparation method thereof - Google Patents
Sodium ion battery anode material precursor and preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 35
- 239000002243 precursor Substances 0.000 title claims abstract description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 17
- 239000011572 manganese Chemical class 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 abstract description 9
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A precursor of a positive electrode material of a sodium ion battery has a chemical formula of Cu x Fe y Mn 1‑x‑y (OH) 2 The preparation method comprises the following steps: 1. preparing a first mixed solution of Cu salt and Mn salt; preparing sodium hydroxide or potassium hydroxide solution as a precipitator; preparing a first complexing agent solution; preparing a second mixed solution of Fe salt and a second complexing agent; preparing an additive solution; 2. adding pure water, a precipitator and a first complexing agent solution into a kettle to prepare a base solution; 3. introducing protective gas, and adding the first mixed solution, the second mixed solution, the precipitant, the first complexing agent solution and the additive solution into a kettle for coprecipitation; 4. and carrying out filter pressing, washing and drying on the product to obtain a loose and porous sodium ion battery anode material precursor. The positive electrode material prepared by the precursor has high sodium ion diffusion speed and can improve the electrical property.
Description
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to a precursor of a sodium ion battery anode material and a preparation method thereof.
Background
Compared with a lithium ion battery, a sodium ion battery has two advantages: firstly, the cost of raw materials is low, high-valence rare metals such as lithium and cobalt are not used, the greatest advantage of sodium is that the sodium is abundant in resources such as seawater and the like, is an inexhaustible element, and secondly, the existing production process can be used. The working mechanism of the sodium ion battery is the same as that of the lithium battery, and the existing production equipment of a battery enterprise can be directly used for producing the sodium ion battery, so that each enterprise can easily take the sodium ion battery as a substitute battery to carry out production because repeated equipment investment is basically not needed.
As an important component of sodium ion batteries, the performance of the positive electrode material determines the performance of the battery. The ferro-manganese-copper-based positive electrode material is one of the most commercialized sodium ion positive electrode materials because of the attractive attention of a large number of researchers due to the advantages of high energy density and low cost. However, since the radius of sodium ions is larger than that of lithium ions, the diffusion rate in the positive electrode material is much slower, resulting in a decrease in electrical properties.
Therefore, how to solve the above-mentioned drawbacks of the prior art is a subject to be studied and solved by the present invention.
Disclosure of Invention
The invention aims to provide a precursor of a positive electrode material of a sodium ion battery and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a precursor of a positive electrode material of a sodium ion battery has a chemical formula of Cu x Fe y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.1 and less than or equal to 0.4,0.2, and y is more than or equal to 0.5.
The relevant content explanation in the technical scheme is as follows:
1. in the scheme, D50 is 5-8 um, the granularity diameter distance is 0.70 < (D90-D10)/D50 is less than 0.85, and the tap density is 1.00-1.35 g/cm 3 Specific surface area of 70-120 m 2 G, the porosity is 30-60%;
the network skeleton of the precursor is a loose sheet-shaped cross-linked structure, tiny particles are filled in the skeleton, the size of the tiny particles is 100-300 nm, and the thickness of a loose sheet is 50-150 nm.
In order to achieve the purpose, the technical scheme adopted in the method level of the invention is as follows:
a preparation method of a precursor of a positive electrode material of a sodium ion battery comprises the following steps:
preparing a first mixed solution of Cu salt and Mn salt, wherein the total concentration of Cu and Mn is 110-125 g/L;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitator;
preparing a first complexing agent solution with the molar concentration of 2-4 mol/L, wherein the first complexing agent comprises one or more of ammonia water and ammonium sulfate;
preparing a second mixed solution of Fe salt and a second complexing agent, wherein the concentration of Fe is 55-65 g/L, and the concentration of the second complexing agent is 2-10 g/L;
preparing an additive solution with the mass fraction of 0.8-1.2%;
adding pure water, the precipitant and the first complexing agent solution into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.8-12.3 through the precipitant, controlling the ammonia concentration in the base solution to be 0.15-0.35 mol/L through the first complexing agent, and maintaining the temperature of the base solution to be 50-70 ℃;
step three, keeping the reaction kettle stirred and opened, introducing protective gas into the reaction system, simultaneously adding the first mixed solution, the second mixed solution, the precipitant, the first complexing agent solution and the additive solution in the step one into the reaction kettle to perform coprecipitation reaction, stopping liquid feeding when the target granularity D50 is grown, and completing the coprecipitation reaction;
in the reaction process, the pH of the system is adjusted from 11.8 to 12.3 to 11.3 to 11.8 every hour, the stirring speed is 200 to 500rpm, the reaction time is 30 to 60 hours, the concentration of complexing agent in the reaction kettle is 0.15 to 0.35mol/L, the synthesis temperature is maintained at 50 to 70 ℃, and the mass fraction of additives in the reaction kettle is 0.02 to 0.06 percent;
and step four, carrying out filter pressing, washing and drying on the coprecipitation product in the step three to obtain a loose and porous sodium ion battery anode material precursor.
The relevant content explanation in the technical scheme is as follows:
1. in the above scheme, the target particle size D50 is 5-8 um.
2. In the above solution, in the first step, the Cu salt includes any one or a combination of at least two of copper sulfate, copper chloride, and copper nitrate;
the Mn salt comprises any one or a combination of at least two of manganese sulfate, manganese chloride and manganese nitrate;
the Fe salt comprises any one or a combination of at least two of ferrous sulfate, ferrous chloride and ferrous nitrate.
3. In the above scheme, in the first step, the additive comprises one or more of acrylic acid, oxalic acid and acetic acid.
4. In the above scheme, in the first step, the second complexing agent comprises one or more of sodium citrate and EDTA.
5. In the above scheme, the "concentration of the complexing agent in the reaction kettle" refers to the first complexing agent and the second complexing agent.
6. In the above scheme, the chemical formula of the precursor is Cu x Fe y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.1 and less than or equal to 0.4,0.2, and y is more than or equal to 0.5.
7. In the scheme, D50 is 5-8 um, the granularity diameter distance is 0.70 < (D90-D10)/D50 is less than 0.85, and the tap density is 1.00-1.35 g/cm 3 Specific surface area of 70-120 m 2 And/g, wherein the porosity is 30-60%, the precursor network skeleton is of a loose sheet-shaped cross-linked structure, tiny particles are filled in the skeleton, the size of the tiny particles is 100-300 nm, and the thickness of a loose sheet is 50-150 nm.
The working principle and the advantages of the invention are as follows:
1. according to the invention, the additive solution with the mass fraction of 0.8-1.2% is added in the process of preparing the precursor, and the mass fraction of the additive in the reaction kettle is kept to be 0.02-0.06%. The addition of the additive is beneficial to promoting the precursor network skeleton to form a loose flaky cross-linked structure, and simultaneously ensures that tiny particles can be filled in the skeleton.
2. According to the invention, the second complexing agent with the concentration of 2-10 g/L is added into the Fe salt solution, so that the uniform precipitation of three elements of Fe, cu and Mn on the atomic layer is realized, and the purity of the material is improved.
3. The porosity of the precursor of the positive electrode material of the sodium ion battery prepared by the invention is 30-60%, and the high porosity is beneficial to the diffusion of sodium ions and improves the transmission efficiency of sodium ions.
Drawings
FIG. 1 is an SEM image of a precursor of a positive electrode material of a sodium ion battery prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a precursor of a positive electrode material of a sodium ion battery prepared in example 2 of the present invention;
fig. 3 is a graph showing the rate performance test of the positive electrode materials for sodium ion batteries prepared in examples 1 and 2 of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples:
the present invention will be described in detail with reference to the drawings, wherein modifications and variations are possible in light of the teachings of the present invention, without departing from the spirit and scope of the present invention, as will be apparent to those of skill in the art upon understanding the embodiments of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the terms "comprising," "including," "having," and the like are intended to be open-ended terms, meaning including, but not limited to.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
Example 1:
a preparation method of a precursor of a positive electrode material of a sodium ion battery comprises the following steps:
step one, preparing CuSO 4 、MnSO 4 Wherein the total concentration of Cu and Mn is 120g/L;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 9mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 3mol/L as a first complexing agent;
preparing FeSO 4 A second mixed solution with EDTA, wherein FeSO 4 The concentration of the second complexing agent EDTA is 60g/L, and the concentration of the second complexing agent EDTA is 5g/L;
preparing an acrylic acid solution with the mass fraction of 1% as an additive;
adding pure water, the precipitator and the first complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.8-12.3 through the precipitator, controlling the ammonia concentration in the base solution to be 0.25mol/L through the first complexing agent, and maintaining the temperature of the base solution at 60 ℃;
step three, keeping the reaction kettle stirred and opened, introducing protective gas into the reaction system, adding the first mixed solution, the second mixed solution, the precipitant, the first complexing agent and the additive in the step one into the reaction kettle in parallel flow for coprecipitation reaction, stopping liquid feeding when the particle size D50 is reached, and completing the coprecipitation reaction;
in the reaction process, the pH of the system is adjusted from 11.8 to 12.3 to 11.3 to 11.8 every hour, the stirring speed is 400rpm, the reaction time is 50 hours, the concentration of a complexing agent in a reaction kettle is 0.25mol/L, the synthesis temperature is maintained at 60 ℃, and the mass fraction of an additive in the reaction kettle is 0.05%;
step four, the coprecipitation product in the step three is subjected to filter pressing, washing and drying to obtain a loose and porous sodium ion battery anode material precursor, wherein the chemical formula of the product is Cu 0.25 Fe 0.45 Mn 0.35 (OH) 2 The D50 is 6.89um, the granularity diameter distance is 0.75, and the tap density is 1.15g/cm 3 A specific surface area of 99.6m 2 And/g, porosity 40%. The precursor network skeleton is a loose sheet-shaped cross-linked structure, tiny particles are filled in the skeleton, the size of the tiny particles is 100-300 nm, the thickness of a loose sheet is 50-150 nm, and relevant data are shown in table 1.
Comparative example 1:
the difference from example 1 is that in the first step, the concentration of EDTA as the second complexing agent in the second mixed solution is different, EDTA is not added to the second mixed solution in this comparative example 1, and the rest is the same as in example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 2:
the difference from example 1 is that the amount of acrylic acid added in the third step is different, acrylic acid is not added in this comparative example 2, and the remainder is the same as in example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Example 2:
a method for preparing a precursor of a positive electrode material of a sodium ion battery, comprising:
step one, preparing CuSO 4 、MnSO 4 Wherein the total concentration of Cu and Mn is 120g/L;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 9mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 3mol/L as a first complexing agent;
preparing FeSO 4 A second mixed solution with EDTA, wherein FeSO 4 The concentration of the second complexing agent EDTA is 60g/L, and the concentration of the second complexing agent EDTA is 5g/L;
preparing an acrylic acid solution with the mass fraction of 1% as an additive;
adding pure water, the precipitator and the first complexing agent into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.8-12.3 through the precipitator, controlling the ammonia concentration in the base solution to be 0.25mol/L through the first complexing agent, and maintaining the temperature of the base solution at 60 ℃;
step three, keeping the reaction kettle stirred and opened, introducing protective gas into the reaction system, adding the first mixed solution, the second mixed solution, the precipitant, the first complexing agent and the additive in the step one into the reaction kettle in parallel flow for coprecipitation reaction, stopping liquid feeding when the particle size D50 is reached, and completing the coprecipitation reaction;
in the reaction process, the pH of the system is adjusted from 11.8 to 12.3 to 11.3 to 11.8 every hour, the stirring speed is 400rpm, the reaction time is 50 hours, the concentration of a complexing agent in a reaction kettle is 0.25mol/L, the synthesis temperature is maintained at 60 ℃, and the mass fraction of an additive in the reaction kettle is 0.05%;
step four, the coprecipitation product in the step three is subjected to filter pressing, washing and drying to obtain a loose and porous sodium ion battery anode material precursor, wherein the chemical formula of the product is Cu 0.35 Fe 0.45 Mn 0.20 (OH) 2 The D50 is 7.45um, the granularity diameter distance is 0.74, and the tap density is 1.20g/cm 3 A specific surface area of 78.6m 2 And/g, the porosity is 55%. The precursor network skeleton is a loose sheet-shaped cross-linked structure, tiny particles are filled in the skeleton, the size of the tiny particles is 100-300 nm, the thickness of a loose sheet is 50-150 nm, and relevant data are shown in table 1.
Table 1 shows the data of the products obtained in each example and each comparative example.
From the data in table 1, it can be seen that: the addition of the acrylic acid is beneficial to promoting the precursor network skeleton to form a loose flaky cross-linked structure, and simultaneously promoting tiny particles to be filled in the skeleton, and the structure is beneficial to improving the diffusion rate of sodium ions and improving the electrical property. The precursor prepared without sodium acrylate (comparative example 2) was relatively dense inside, resulting in a decrease in specific surface area, which is detrimental to the diffusion of sodium ions. EDTA is added into the mixed solution D to promote the uniform precipitation of three elements of Fe, cu and Mn on the atomic layer, so that the purity of the product is improved.
Fig. 1 and fig. 2 are SEM images of a precursor of a positive electrode material of a sodium ion battery prepared in example 1 and example 2, respectively, and it can be seen from the figures that the precursor network skeleton is a loose sheet-shaped cross-linked structure, the skeleton is filled with tiny particles, the size of the tiny particles is 100-300 nm, and the thickness of the loose sheet is 50-150 nm.
Fig. 3 shows the results of the rate performance test of the positive electrode materials of sodium-ion batteries prepared in example 1 and example 2, and it can be seen from the graph that the positive electrode material of sodium-ion battery prepared by the technology of the present invention has the optimal rate performance.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (3)
1. A preparation method of a precursor of a positive electrode material of a sodium ion battery is characterized by comprising the following steps: comprising the following steps:
preparing a first mixed solution of Cu salt and Mn salt, wherein the total concentration of Cu and Mn is 110-125 g/L;
preparing sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitant;
preparing a first complexing agent solution with the molar concentration of 2-4 mol/L, wherein the first complexing agent comprises one or more of ammonia water and ammonium sulfate;
preparing a second mixed solution of Fe salt and a second complexing agent, wherein the concentration of Fe is 55-65 g/L, the second complexing agent is EDTA, and the concentration is 5g/L;
preparing an acrylic acid solution with the mass fraction of 1% as an additive;
adding pure water, the precipitant and the first complexing agent solution into a closed reaction kettle to prepare a base solution, controlling the pH value of the base solution to be 11.8-12.3 through the precipitant, controlling the ammonia concentration in the base solution to be 0.15-0.35 mol/L through the first complexing agent, and maintaining the temperature of the base solution to be 50-70 ℃;
step three, keeping a reaction kettle stirring and opening, introducing protective gas into a reaction system, simultaneously adding the first mixed solution, the second mixed solution, the precipitant, the first complexing agent solution and the additive solution in the step one into the reaction kettle to perform coprecipitation reaction, stopping feeding liquid when the target granularity is grown, and completing the coprecipitation reaction;
in the reaction process, the pH of the system is adjusted from 11.8 to 12.3 to 11.3 to 11.8 every hour, the stirring speed is 200 to 500rpm, the reaction time is 30 to 60 hours, the concentration of a complexing agent in a reaction kettle is 0.15 to 0.35mol/L, the synthesis temperature is maintained at 50 to 70 ℃, and the mass fraction of an additive in the reaction kettle is 0.02 to 0.06 percent;
step four, the coprecipitation product in the step three is subjected to filter pressing, washing and drying to obtain loose and porous sodium ion battery anode material precursor;
the chemical formula of the precursor is Cu x Fe y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.1 and less than or equal to 0.4,0.2, and y is more than or equal to 0.5.
2. The method of manufacturing according to claim 1, characterized in that: in the first step, the Cu salt comprises any one or a combination of at least two of copper sulfate, copper chloride and copper nitrate;
the Mn salt comprises any one or a combination of at least two of manganese sulfate, manganese chloride and manganese nitrate;
the Fe salt comprises any one or a combination of at least two of ferrous sulfate, ferrous chloride and ferrous nitrate.
3. The method of manufacturing according to claim 1, characterized in that: the D50 is 5-8 um, the granularity diameter distance is 0.70 < (D90-D10)/D50 is less than 0.85, and the tap density is 1.00-1.35 g/cm 3 Specific surface area of 70-120 m 2 And/g, wherein the porosity is 30-60%, the precursor network skeleton is of a loose sheet-shaped cross-linked structure, tiny particles are filled in the skeleton, the size of the tiny particles is 100-300 nm, and the thickness of a loose sheet is 50-150 nm.
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