CN116462242A - Nickel-iron-manganese-copper sodium ion precursor and preparation method and application thereof - Google Patents
Nickel-iron-manganese-copper sodium ion precursor and preparation method and application thereof Download PDFInfo
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- CN116462242A CN116462242A CN202310667047.2A CN202310667047A CN116462242A CN 116462242 A CN116462242 A CN 116462242A CN 202310667047 A CN202310667047 A CN 202310667047A CN 116462242 A CN116462242 A CN 116462242A
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- 239000002243 precursor Substances 0.000 title claims abstract description 52
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 44
- -1 Nickel-iron-manganese-copper sodium Chemical compound 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 150000001879 copper Chemical class 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000975 co-precipitation Methods 0.000 claims abstract description 29
- 239000008139 complexing agent Substances 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 28
- 239000012266 salt solution Substances 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 17
- OANFWJQPUHQWDL-UHFFFAOYSA-N copper iron manganese nickel Chemical compound [Mn].[Fe].[Ni].[Cu] OANFWJQPUHQWDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 claims abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 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 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- RMZMFASTOVOJPY-UHFFFAOYSA-N [Fe].[Mn].[Ni].[Na] Chemical compound [Fe].[Mn].[Ni].[Na] RMZMFASTOVOJPY-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052748 manganese Inorganic materials 0.000 abstract description 12
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 229910052759 nickel Inorganic materials 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- BQCFCWXSRCETDO-UHFFFAOYSA-N [Fe].[Mn].[Cu] Chemical compound [Fe].[Mn].[Cu] BQCFCWXSRCETDO-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000002431 foraging effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000012066 reaction slurry Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PNFQFZXRHXDPDK-UHFFFAOYSA-N [O-2].[Fe+2].[Cu+2].[Mn+2].[O-2].[O-2] Chemical compound [O-2].[Fe+2].[Cu+2].[Mn+2].[O-2].[O-2] PNFQFZXRHXDPDK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M4/48—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
-
- 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
-
- 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
- C01P2006/40—Electric properties
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a nickel-iron-manganese-copper sodium ion precursor, and a preparation method and application thereof. The preparation method comprises the following steps: adding a nickel-iron-manganese mixed salt solution, a copper salt solution, a precipitant solution and a complexing agent solution into a base solution in parallel flow, and performing coprecipitation reaction to obtain the nickel-iron-manganese-copper sodium ion precursor; wherein the copper salt solution also comprises a dispersing agent. According to the invention, under a nickel-iron-manganese-copper coprecipitation system, copper salt is singly added and contains a dispersing agent, the dispersing agent can be matched with a complexing agent, the uniformity of reaction is maintained, copper, nickel, iron and manganese are promoted to be uniformly precipitated, and a precursor material with uniform precipitation of elements and stable and compact structure is obtained.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a nickel-iron-manganese-copper sodium ion precursor, and a preparation method and application thereof.
Background
Due to the natural cost advantages of the sodium ion battery, the technology is broken through continuously, the comprehensive performance is improved continuously, and the industrialization process is accelerated. Among three commonly used positive electrode materials of the sodium ion battery, the manufacturing process cost of the vanadium-containing polyanion series is higher, and the cost of the sulfate polyanion material is controllable and is a sodium storage material with great potential, and the sodium storage material is currently being developed; prussian series materials are sufficient but contain crystallization water which is difficult to remove, and the problems of crystallization integrity and the like of the materials are faced; the layered oxide positive electrode material has excellent comprehensive performance, and the manufacturing process thereof is highly overlapped with the ternary lithium battery positive electrode, so that industrialization is realized first.
The sodium ion battery layered oxide positive electrode material iron-manganese-copper gene has the advantages of high energy density and low cost, and becomes a research hot spot.
CN115188958A discloses a preparation method of spherical porous sodium ion battery material, comprising: mixing salt solutions of ferric salt, cupric salt and divalent manganese salt with glycerol for hydrothermal reaction, and washing and drying to obtain a carbonate precursor containing iron, copper and manganese; presintering a carbonate precursor of the iron, copper and manganese to obtain a three-element iron, copper and manganese oxide; and mixing and calcining the ternary iron-copper-manganese oxide and sodium carbonate to obtain the sodium ion battery material. This document discloses a method for preparing iron-copper-manganese precursors but the use of hydrothermal reaction requires high-pressure equipment, which requires high cost and high operational risk, which is disadvantageous for mass production.
Meanwhile, in an iron-manganese-copper coprecipitation reaction system, copper phase separation is very easy to occur due to the addition of copper element. For example, CN114050257A provides a ferromanganese anode precursor material, a preparation method and application thereof. The chemical formula of the positive electrode precursor material is Mn X Cu Y Fe 1-X-Y (OH) 3-X-Y Wherein X is more than 0.3 and less than 0.45,0.1 and Y is more than 0.4. The preparation method of the precursor material is a coprecipitation method, and comprises the following steps: mixing an iron source, a copper source and a complexing agent to obtain a metal complexing solution, and adding the metal complexing solution, a manganese source and a precipitator into a base solution in parallel flow, wherein the base solution comprises a reducing agent and the complexing agent, and performing coprecipitation reaction to obtain the ferromanganese anode precursor material.
Therefore, how to obtain a sodium ion precursor material with uniformly precipitated elements is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a nickel-iron-manganese-copper sodium ion precursor, and a preparation method and application thereof. According to the invention, under a nickel-iron-manganese-copper coprecipitation system, copper salt is singly added and contains a dispersing agent, the dispersing agent can be matched with a complexing agent, the uniformity of reaction is maintained, copper, nickel, iron and manganese are promoted to be uniformly precipitated, and a precursor material with uniform precipitation of elements and stable and compact structure is obtained.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a precursor of nickel-iron-manganese-copper sodium ions, the method comprising the steps of:
the preparation process provided by the invention is carried out in a protective atmosphere, so that no reducing agent is required to be added in the preparation process.
Adding a nickel-iron-manganese mixed salt solution, a copper salt solution, a precipitant solution and a complexing agent solution into a base solution in parallel flow, and performing coprecipitation reaction to obtain the nickel-iron-manganese-copper sodium ion precursor;
wherein the copper salt solution also comprises a dispersing agent.
According to the invention, under a nickel-iron-manganese-copper coprecipitation system, copper salt is singly added and contains a dispersing agent, the dispersing agent can be matched with a complexing agent, the uniformity of reaction is maintained, copper, nickel, iron and manganese are promoted to be uniformly precipitated, and a precursor material with uniform precipitation of elements and stable and compact structure is obtained.
In the invention, if the dispersing agent is not added into the copper salt solution, and only copper salt is fed independently, the condition that Cu is separated out independently is aggravated, and coprecipitation cannot be realized.
Preferably, the total concentration of metal ions in the ferronickel manganese mixed salt solution is 90-120 g/L, such as 90g/L, 100g/L, 110g/L or 120g/L, etc.
Preferably, the concentration of the copper salt solution is 20 to 50g/L, for example 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, etc.
Preferably, in the copper salt solution, the mass of the dispersant is 0.05 to 2% of the mass of the copper metal, for example, 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8% or 2% or the like.
In the invention, too little mass of the dispersant in the copper salt solution can cause high supersaturation degree and phase separation condition, and too much dispersant can cause poor crystallinity of particles and too much impurity content.
Preferably, the dispersing agent comprises any one or a combination of at least two of polyethylene glycol, cetyl trimethyl ammonium bromide, alkyl phosphate, disodium ethylenediamine tetraacetate, crown ether or amino acid, preferably polyethylene glycol.
Preferably, the concentration of the precipitant is 250 to 300g/L, for example 250g/L, 260g/L, 270g/L, 280g/L, 290g/L or 300g/L, etc.
Preferably, the precipitating agent comprises sodium carbonate.
Preferably, the complexing agent is present in a concentration of 100 to 300g/L, for example 100g/L, 130g/L, 150g/L, 180g/L, 200g/L, 230g/L, 250g/L, 280g/L or 300g/L, etc.
In the invention, the concentration range of the complexing agent of 100-300 g/L is the concentration of the solution of each complexing agent in the complexing agents.
Preferably, the complexing agent comprises ammonia and/or ammonium bicarbonate, preferably ammonia and ammonium bicarbonate.
In the invention, the mixed solution of ammonia water and ammonium bicarbonate is selected as a complexing agent, and can be used in a synergistic effect with a dispersing agent, and the ammonia water and the ammonium bicarbonate are mixed for use as a buffer system solution, so that the pH can be stabilized, the complexing metal element can be realized, and uniform coprecipitation can be realized.
Preferably, the base liquid comprises water, a precipitant and a complexing agent.
Preferably, the pH of the base liquid is from 10 to 11, such as 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9 or 11, etc.
Preferably, the pH during the coprecipitation reaction is 8 to 10, for example 8, 8.3, 8.5, 8.8, 9, 9.3, 9.5, 9.8 or 10, etc.
Preferably, the reaction temperature during the coprecipitation reaction is 30 to 70 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, or the like.
Preferably, the stirring rate during the coprecipitation reaction is 180 to 400rpm, for example 180rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm or the like.
Preferably, the reaction is stopped after the coprecipitation reaction is performed until the target particle diameter of the particles is 5 to 18. Mu.m, for example, 5. Mu.m, 6. Mu.m, 7. Mu.m, 8. Mu.m, 9. Mu.m, 10. Mu.m, 11. Mu.m, 12. Mu.m, 13. Mu.m, 14. Mu.m, 15. Mu.m, 16. Mu.m, 17. Mu.m, 18. Mu.m, etc.
Preferably, after the coprecipitation reaction is finished, aging, filtering, washing and drying are sequentially performed.
Preferably, the aging time is 2 to 15 hours, such as 2 hours, 5 hours, 10 hours, 15 hours, etc.
As a preferred technical scheme, the preparation method comprises the following steps:
adding a nickel-iron-manganese mixed salt solution with the total concentration of metal ions of 90-120 g/L, a copper salt solution with the concentration of 20-50 g/L, a precipitant solution with the concentration of 250-300 g/L and a complexing agent solution with the concentration of 100-300 g/L into a base solution in parallel, keeping the pH value of 8-10, carrying out coprecipitation reaction at the stirring speed of 180-400 rpm at the temperature of 30-70 ℃ until the target particle size is 5-18 mu m, stopping the reaction, and sequentially carrying out aging, filtering, washing and drying to obtain the nickel-iron-manganese-copper sodium ion precursor;
wherein the copper salt solution also comprises a dispersing agent, and the mass of the dispersing agent in the copper salt solution is 0.05-2% of the mass of copper metal.
In a second aspect, the invention provides a nickel iron manganese copper sodium ion precursor prepared by the preparation method according to the first aspect.
Preferably, the chemical formula of the nickel-iron-manganese-copper sodium ion precursor is Ni 1-x-y-z Cu x Fe y Mn z CO 3 Where 0.1+.x+. 0.2,0.1 +.y+. 0.25,0.1 +.z+.0.25, for example, the x can be 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 or 0.2, etc., the y can be 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2 or 0.25, etc., the z can be 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2 or 0.25, etc.
In a third aspect, the invention provides a sodium ion positive electrode material, which is obtained by mixing and sintering the nickel-iron-manganese-copper sodium ion precursor according to the second aspect and a sodium source.
In a fourth aspect, the present invention also provides a sodium ion battery comprising a sodium ion positive electrode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, under a nickel-iron-manganese-copper coprecipitation system, copper salt is singly added and contains a dispersing agent, the dispersing agent can be matched with a complexing agent, the uniformity of reaction is maintained, copper, nickel, iron and manganese are promoted to be uniformly precipitated, and a precursor material with uniform precipitation of elements and stable and compact structure is obtained. The positive electrode material in the battery is prepared by adopting the precursor material lifted by the invention, after the battery is activated for 2 circles at 0.1C/0.1C under the voltage range of 2-4.2V, the initial circle capacity at 0.2C can reach 138mAh/g or more, and the capacity retention rate after 100 circles at 0.5C can reach 85% or more.
Drawings
Fig. 1 is an SEM image of a sodium nickel iron manganese copper precursor provided in example 1.
Fig. 2 is an SEM image of the sodium nickel iron manganese copper ion precursor provided in comparative example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a nickel-iron-manganese-copper sodium ion precursor, and the preparation method of the precursor comprises the following steps:
step 1, preparing a first mixed solution of nickel salt, iron salt and manganese salt (the molar ratio of nickel to iron to manganese to copper is 0.7:0.1:0.1:0.1 in sequence, and the mixed solution is sulfate solution), wherein the total metal concentration of the mixed solution is 115g/L; preparing copper salt (copper sulfate) with the concentration of 35g/L, adding polyethylene glycol into the copper salt, stirring and mixing uniformly to obtain a second mixed solution, wherein the amount of the polyethylene glycol is 1% of the mass of copper metal; preparing a sodium carbonate solution (precipitant solution) with the concentration of 250 g/L; preparing a third mixed solution (complexing agent solution) of ammonia water with the concentration of 150g/L and 220g/L ammonium bicarbonate;
step 2, adding pure water, sodium carbonate solution and a third mixed solution into a sealed reaction kettle as base solution, wherein the pH value of the base solution is 10.5, the ammonia concentration is 12g/L, the reaction temperature is 50 ℃, and the stirring rotation speed is 350rpm;
step 3, the first mixed solution, the second mixed solution, the sodium carbonate solution and the third mixed solution are added into the base solution of the reaction kettle in parallel, and are continuously stirred to carry out coprecipitation reaction, wherein the pH value is maintained at 8.5, the ammonia concentration is 12g/L, the reaction temperature is controlled at 50 ℃, the stirring rotation speed is controlled at 350rpm, and the feeding is stopped when the reaction kettle grows to 12 mu m, so that the reaction is completed;
step 4, placing the reaction slurry into an aging tank for aging for 6 hours, and then sequentially filtering, washing and drying to obtain a sodium ion nickel-manganese-iron-copper quaternary precursor (Ni 0.7 Cu 0.1 Fe 0.1 Mn 0.1 CO 3 )。
Example 2
The embodiment provides a nickel-iron-manganese-copper sodium ion precursor, and the preparation method of the precursor comprises the following steps:
step 1, preparing a first mixed solution of nickel salt, iron salt and manganese salt (the molar ratio of nickel to iron to manganese to copper is 0.7:0.1:0.1:0.1 in sequence, and the mixed solution is sulfate solution), wherein the total metal concentration of the mixed solution is 90g/L; preparing copper salt (copper sulfate) with the concentration of 20g/L, adding polyethylene glycol into the copper salt, stirring and mixing uniformly to obtain a second mixed solution, wherein the amount of the polyethylene glycol is 2% of the mass of copper metal; preparing a sodium carbonate solution (precipitant solution) with the concentration of 250 g/L; preparing a third mixed solution (complexing agent solution) of ammonia water and ammonium bicarbonate with the concentration of 250 g/L;
step 2, adding pure water, sodium carbonate solution and a third mixed solution into a sealed reaction kettle as base solution, wherein the pH value of the base solution is 10.5, the ammonia concentration is 15g/L, the reaction temperature is 40 ℃, and the stirring rotation speed is 200rpm;
step 3, the first mixed solution, the second mixed solution, the sodium carbonate solution and the third mixed solution are added into the base solution of the reaction kettle in parallel, and are continuously stirred to carry out coprecipitation reaction, wherein the pH value is maintained at 9.5, the ammonia concentration is 15g/L, the reaction temperature is controlled at 40 ℃, the stirring rotating speed is controlled at 200rpm, and the feeding is stopped when the reaction kettle grows to 10 mu m, so that the reaction is completed;
step 4, placing the reaction slurry into an aging tank for aging for 6 hours, and then sequentially filtering, washing and drying to obtain a sodium ion nickel-manganese-iron-copper quaternary precursor (Ni 0.7 Cu 0.1 Fe 0.1 Mn 0.1 CO 3 )。
Example 3
The embodiment provides a nickel-iron-manganese-copper sodium ion precursor, and the preparation method of the precursor comprises the following steps:
step 1, preparing a first mixed solution of nickel salt, iron salt and manganese salt (the molar ratio of nickel to iron to manganese to copper is 0.45:0.15:0.25:0.15 in sequence, and the mixed solution is sulfate solution), wherein the total metal concentration of the mixed solution is 115g/L; preparing copper salt (copper sulfate) with the concentration of 35g/L, adding amino acid into the copper salt, stirring and uniformly mixing to obtain a second mixed solution, wherein the amount of the amino acid is 0.05% of the mass of copper metal; preparing a sodium carbonate solution (precipitant solution) with the concentration of 250 g/L; preparing a third mixed solution (complexing agent solution) of ammonia water and ammonium bicarbonate with the concentration of 200 g/L;
step 2, adding pure water, sodium carbonate solution and a third mixed solution into a sealed reaction kettle as base solution, wherein the pH value of the base solution is 10.5, the ammonia concentration is 12g/L, the reaction temperature is 50 ℃, and the stirring rotation speed is 350rpm;
step 3, the first mixed solution, the second mixed solution, the sodium carbonate solution and the third mixed solution are added into the base solution of the reaction kettle in parallel, and are continuously stirred to carry out coprecipitation reaction, wherein the pH value is maintained at 8.5, the ammonia concentration is 12g/L, the reaction temperature is controlled at 50 ℃, the stirring rotation speed is controlled at 350rpm, and the feeding is stopped when the reaction kettle grows to 12 mu m, so that the reaction is completed;
step 4, placing the reaction slurry into an aging tank for aging for 6 hours, and then sequentially filtering, washing and drying to obtain a sodium ion nickel-manganese-iron-copper quaternary precursor (Ni 0.45 Cu 0.15 Fe 0.25 Mn 0.15 CO 3 )。
Example 4
The difference between this example and the example is that in step 1 of this example, polyethylene glycol is 2.5% of the mass of copper metal.
The remaining preparation methods and parameters were consistent with example 1.
Example 5
The difference between this example and example 1 is that the complexing agent solution in this example is a pure aqueous ammonia solution.
The remaining preparation methods and parameters were consistent with example 1.
Example 6
The difference between this example and example 1 is that the complexing agent solution in this example is a pure ammonium bicarbonate solution.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The difference between this comparative example and example 1 is that polyethylene glycol was not added in step 1 of this comparative example.
The remaining preparation methods and parameters were consistent with example 1.
Fig. 1 and 2 show SEM images of the nickel-iron-manganese-copper sodium ion precursors provided in example 1 and comparative example 1, respectively, and it can be seen from fig. 1 and 2 that the metal elements can be completely co-precipitated with the dispersant, and the surface is compact and no impurity phase is separated out.
The sodium ion precursor materials provided in examples 1 to 6 and comparative example 1 were mixed with sodium carbonate and sintered at 1000 ℃ for 12 hours, and the obtained materials were subjected to pulverization treatment to obtain a sodium ion oxide positive electrode material.
Homogenizing the provided sodium ion positive electrode material serving as a main material according to the proportion of 95 (main material): 2.5 (PVDF): 2.5 (SP), spreading an aluminum foil on a coater for coating, and drying in a blast drying oven at 120 ℃ for 3 hours; then punching, weighing, baking the pole piece, manufacturing a CR2032 button cell, and finally placing the cell into a blue electric testing system for electric performance testing.
The batteries provided in examples 1 to 6 and comparative example 1 were subjected to electrochemical performance testing under the following conditions: capacity test at 2-4.2V voltage range: 0.1C/0.1C activation 2 cycles, 0.2C/0.2C resulting capacity; and (3) cyclic test: the capacity retention obtained at 100 cycles of 0.5C/0.5C was measured and the test results are shown in Table 1.
TABLE 1
| First circle capacity (mAh/g) | Cycle retention (%) | |
| Example 1 | 150 | 92 |
| Example 2 | 146 | 90 |
| Example 3 | 145 | 90 |
| Example 4 | 138 | 85 |
| Example 5 | 140 | 89 |
| Example 6 | 142 | 89 |
| Comparative example 1 | 110 | 80 |
From the data of examples 1 and 4, it is clear that too much dispersant is added to introduce more impurities, which affects the cycle performance.
From the data of examples 1 and 5 and 6, it is clear that neither pure aqueous ammonia complexing agent nor pure sodium bicarbonate complexing agent achieves complete co-precipitation, resulting in poor capacity and circulation.
As is clear from the data of example 1 and comparative example 1, the copper phase separation problem cannot be solved without adding a dispersant to the copper salt solution added alone.
In conclusion, under the nickel-iron-manganese-copper coprecipitation system, copper salt is singly added and contains dispersing agent, the dispersing agent can be matched with complexing agent, uniformity of reaction is maintained, copper, nickel, iron and manganese are promoted to be uniformly precipitated, and precursor materials with uniform precipitation of elements and stable and compact structure are obtained. The positive electrode material in the battery is prepared by adopting the precursor material lifted by the invention, after the battery is activated for 2 circles at 0.1C/0.1C under the voltage range of 2-4.2V, the initial circle capacity at 0.2C can reach 138mAh/g or more, and the capacity retention rate after 100 circles at 0.5C can reach 85% or more.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The preparation method of the nickel-iron-manganese-copper sodium ion precursor is characterized by comprising the following steps of:
adding a nickel-iron-manganese mixed salt solution, a copper salt solution, a precipitant solution and a complexing agent solution into a base solution in parallel flow, and performing coprecipitation reaction to obtain the nickel-iron-manganese-copper sodium ion precursor;
wherein the copper salt solution also comprises a dispersing agent.
2. The method for preparing a nickel-iron-manganese-copper sodium ion precursor according to claim 1, wherein the total concentration of metal ions in the nickel-iron-manganese mixed salt solution is 90-120 g/L;
preferably, the concentration of the copper salt solution is 20-50 g/L;
preferably, in the copper salt solution, the mass of the dispersing agent is 0.05-2% of the mass of copper metal;
preferably, the dispersing agent comprises any one or a combination of at least two of polyethylene glycol, cetyl trimethyl ammonium bromide, alkyl phosphate, disodium ethylenediamine tetraacetate, crown ether or amino acid, preferably polyethylene glycol.
3. The method for preparing a precursor of nickel-iron-manganese-copper sodium ions according to claim 1 or 2, wherein the concentration of the precipitant is 250-300 g/L;
preferably, the precipitating agent comprises sodium carbonate;
preferably, the concentration of the complexing agent is 100-300 g/L;
preferably, the complexing agent comprises ammonia and/or ammonium bicarbonate, preferably ammonia and ammonium bicarbonate.
4. A method of preparing a precursor of nickel-iron-manganese-copper sodium ions according to any one of claims 1 to 3, wherein the base solution comprises water, a precipitant and a complexing agent;
preferably, the pH value of the base solution is 10-11.
5. The method for preparing a precursor of nickel-iron-manganese-copper sodium ion according to any one of claims 1 to 4, wherein the pH value during the coprecipitation reaction is 8 to 10;
preferably, the reaction temperature in the coprecipitation reaction process is 30-70 ℃;
preferably, the stirring speed in the coprecipitation reaction process is 180-400 rpm;
preferably, after the coprecipitation reaction is carried out until the target particle diameter of the particles is 5-18 mu m, stopping the reaction;
preferably, after the coprecipitation reaction is finished, aging, filtering, washing and drying are sequentially carried out;
preferably, the aging time is 2 to 15 hours.
6. The method for preparing a precursor of sodium ion of nickel-iron-manganese-copper according to any one of claims 1 to 5, comprising the steps of:
adding a nickel-iron-manganese mixed salt solution with the total concentration of metal ions of 90-120 g/L, a copper salt solution with the concentration of 20-50 g/L, a precipitant solution with the concentration of 250-300 g/L and a complexing agent solution with the concentration of 100-300 g/L into a base solution in parallel, keeping the pH value of 8-10, carrying out coprecipitation reaction at the stirring speed of 180-400 rpm at the temperature of 30-70 ℃ until the target particle size is 5-18 mu m, stopping the reaction, and sequentially carrying out aging, filtering, washing and drying to obtain the nickel-iron-manganese-copper sodium ion precursor;
wherein the copper salt solution also comprises a dispersing agent, and the mass of the dispersing agent in the copper salt solution is 0.05-2% of the mass of copper metal.
7. A precursor of sodium nickel iron manganese copper ions, wherein the precursor of sodium nickel iron manganese copper ions is prepared by the preparation method according to any one of claims 1-6.
8. The precursor of sodium nickel manganese iron according to claim 7, wherein the precursor of sodium nickel manganese iron has a chemical formula of Ni 1-x-y-z Cu x Fe y Mn z CO 3 Wherein 0.1 +.x +. 0.2,0.1 +.y +. 0.25,0.1 +.z +.0.25.
9. A sodium ion positive electrode material, which is obtained by mixing and sintering the nickel-iron-manganese-copper sodium ion precursor according to claim 7 or 8 and a sodium source.
10. A sodium ion battery comprising the sodium ion positive electrode material of claim 9.
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