CN117049611A - Sodium ion positive electrode precursor material and preparation method and application thereof - Google Patents
Sodium ion positive electrode precursor material and preparation method and application thereof Download PDFInfo
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- CN117049611A CN117049611A CN202311169369.0A CN202311169369A CN117049611A CN 117049611 A CN117049611 A CN 117049611A CN 202311169369 A CN202311169369 A CN 202311169369A CN 117049611 A CN117049611 A CN 117049611A
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 47
- 239000002243 precursor Substances 0.000 title claims abstract description 45
- 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 20
- 239000000243 solution Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000008139 complexing agent Substances 0.000 claims abstract description 31
- UTICYDQJEHVLJZ-UHFFFAOYSA-N copper manganese nickel Chemical compound [Mn].[Ni].[Cu] UTICYDQJEHVLJZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000975 co-precipitation Methods 0.000 claims abstract description 24
- 239000001509 sodium citrate Substances 0.000 claims abstract description 24
- 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 claims abstract description 24
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- 239000011572 manganese Substances 0.000 claims description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000007774 positive electrode material Substances 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 239000010949 copper Substances 0.000 abstract description 27
- 229910052802 copper Inorganic materials 0.000 abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005191 phase separation Methods 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 manganese nickel copper sodium Chemical compound 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000012691 Cu precursor Substances 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a sodium ion positive electrode precursor material, and a preparation method and application thereof. The preparation method comprises the following steps: adding a nickel-copper-manganese mixed salt solution, a precipitator solution and a complexing agent solution in parallel, and carrying out coprecipitation reaction in a protective atmosphere to obtain the nickel-copper-manganese mixed salt solution; wherein the precipitant solution comprises a carbonate system solution and the complexing agent solution comprises a sodium citrate solution. According to the invention, a carbonate system is adopted for coprecipitation reaction, and a special sodium citrate complexing agent is combined, so that the problem of copper phase separation in the coprecipitation reaction process under a nickel-copper-manganese system is solved, the sphericity and consistency of a precursor material are improved, and the specific capacity and the cycling stability of the anode material are improved.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a sodium ion positive electrode precursor material, a preparation method and application thereof.
Background
Due to high specific capacity, the layered transition metal oxide NaTMO is matched with lithium battery equipment, the production process is mature, the comprehensive performance is excellent, and the like 2 There is great interest in the use as positive electrode materials for Sodium Ion Batteries (SIBs). TM is a third period transition metal element (Ti, V, cr, mn, fe, co, ni and Cu) which can be oxidized and reduced, and shows adjustable electrochemical activity through the adjustment of element components and proportions, so that the method is used for flexibly designing new electrode compounds, improving electrochemical performance and meeting specific requirements of downstream application scenes.
A method for preparing a manganese-based sodium ion composite oxide positive electrode material is disclosed in CN107706375 a. The composition general formula of the positive electrode material is Na 1-x Q x Mn 1-y M y O2, wherein x is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.4, and Q and M are both modification elements. The specific method comprises the following steps: a sodium source, a manganese source, and a compound of modifying elements Q and M according to Na: q: mn: m molar ratio is 0.1-1.0: 0 to 0.9:0.5 to 1.0: weighing 0-0.5, loading into equipment with crushing medium and dispersing agent for crushing and uniformly mixing, crystallizing at 500-900 ℃ for 3-30 h for synthesis, cooling to 200-500 ℃, quenching at constant temperature for 1-5 h, naturally cooling to room temperature, and finally mixing and crushing in a mixing and grinding device to obtain the manganese-based sodium ion composite oxide anode material.
Mn 3+ Jahn-Teller distortion of (A) is considered to be O3-NaMnO 2 One of the most important factors in the evolution of the structure, it produces a strong Na ordered phase and creates a unique high capacity new high voltage phase. Mn can act as a promoter and stabilizer for the P2 phase when mixed with other transition metal elements in layered oxides having a composition exceeding 50%. With NaMnO 2 Such P2 phases generally have better circularity and smoother voltage distribution. For some Ni-containing NaTMO 2 A positive electrode for oxygen under a certain high pressure cutoffThe redox process is more reversible and stable than the lithium ion-containing positive electrode. Of particular note, in recent years, environmental-friendly and cost-effective Cu element has been introduced into layered sodium-ion battery cathode materials, which exhibit reversible Cu 2+ / 3+ Redox and capacity, rate capability and cycling stability are enhanced.
After copper is added, the copper is easy to generate phase separation with nickel and manganese elements, so that the sphericity and consistency of the product structure are poor, and the capacity and the cycle performance are poor. For example, CN114956211a relates to a manganese-nickel-copper precursor with different morphology, according to a selected chemical composition, soluble manganese source material, nickel source material and copper source material are taken as raw materials, a precipitant is added to react in the presence of a reducing agent and a complexing agent, the reducing agent comprises at least one of acetaldehyde, phenol or hydrazine hydrate, the complexing agent comprises at least one of ammonia water, sodium fluoride or hydroxyethyl ethylenediamine triacetic acid, the precipitant comprises alkaline solution (sodium hydroxide and potassium hydroxide), copper under the reaction system is extremely easy to phase-separate, and the element distribution is uneven.
Therefore, how to solve the phase separation problem of copper in the precursor of the sodium ion positive electrode material under the nickel-copper-manganese system is a key problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a sodium ion positive electrode precursor material, and a preparation method and application thereof. According to the invention, a carbonate system is adopted for coprecipitation reaction, and a special sodium citrate complexing agent is combined, so that the problem of copper phase separation in the coprecipitation reaction process under a nickel-copper-manganese system is solved, the sphericity and consistency of a precursor material are improved, and the specific capacity and the cycling stability of the anode material are improved.
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 sodium ion positive electrode precursor material, the method comprising the steps of:
adding a nickel-copper-manganese mixed salt solution, a precipitator solution and a complexing agent solution in parallel, and carrying out coprecipitation reaction in a protective atmosphere to obtain the nickel-copper-manganese mixed salt solution;
wherein the precipitant solution comprises a carbonate system solution and the complexing agent solution comprises a sodium citrate solution.
The coprecipitation reaction provided by the invention is carried out in a protective atmosphere (such as nitrogen atmosphere); in the present invention, the salt in the mixed salt solution includes, but is not limited to, sulfate, nitrate, chloride, or the like.
According to the invention, a carbonate system is adopted for coprecipitation reaction, and a special sodium citrate complexing agent, a precipitant and a complexing agent are combined to perform synergistic effect, so that the problem of copper phase separation in the coprecipitation reaction process under a nickel-copper-manganese system is solved, the sphericity and consistency of a precursor material are improved, and the specific capacity and the cycling stability of a positive electrode material are improved.
In the invention, if the precipitant is in a non-carbonate system and is complexed with the sodium citrate complexing agent, the uniform precipitation of Ni, cu and Mn metal elements cannot be realized; however, if other precipitation systems, such as an ammonia water and liquid alkali system, cannot solve the problem of Cu phase separation;
preferably, the total molar concentration of metal ions in the nickel copper manganese mixed salt solution is 0.5-2 mol/L, for example 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L, 1.5mol/L, 1.75mol/L or 2mol/L, etc.
Preferably, the molar concentration of the precipitant solution is 0.5 to 2mol/L, for example 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L, 1.5mol/L, 1.75mol/L or 2mol/L, etc.
Preferably, the complexing agent solution has a molar concentration of 0.25 to 1.5mol/L, for example 0.25mol/L, 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L, 1.5mol/L, etc.
Preferably, the carbonate system solution comprises a sodium carbonate solution and/or a sodium bicarbonate solution.
Preferably, the flow rate of the nickel copper manganese mixed salt solution is 2-10L/h, for example 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h, 8L/h, 9L/h or 10L/h, etc.
Preferably, the flow rate of the precipitant solution is 2 to 8L/h, for example 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h or 8L/h, etc.
Preferably, the complexing agent solution has a flow rate of 1 to 3L/h, such as 1L/h, 1.25L/h, 1.5L/h, 1.75L/h, 2L/h, 2.25L/h, 2.5L/h, 2.75L/h, 3L/h, or the like.
In the invention, the flow of the nickel-copper-manganese mixed salt solution, the flow of the precipitant solution and the flow of the complexing agent solution are synergistic, so that the ion concentration of the system is regulated and controlled, the side reaction in the system is inhibited, and if the flow of any one party is not in the range, the impurity phase is caused.
Preferably, the pH during the co-precipitation reaction is 7.5 to 9.5, e.g. 7, 7.5, 8, 8.5, 9 or 9.5, etc.
Preferably, the stirring speed of the coprecipitation reaction is 230 to 420rpm, for example, 230rpm, 250rpm, 280rpm, 300rpm, 330rpm, 350rpm, 380rpm, 400rpm, 420rpm, or the like.
Preferably, the temperature of the coprecipitation reaction is 30 to 70 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, or the like.
Preferably, the time of the coprecipitation reaction is 40 to 120 hours, for example 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours, 100 hours, 110 hours or 120 hours, etc.
As a preferred technical scheme, the preparation method comprises the following steps:
adding nickel-copper-manganese mixed salt solution with the total molar concentration of metal ions of 0.5-2 mol/L, precipitant solution with the molar concentration of 0.5-2 mol/L and complexing agent solution with the molar concentration of 0.25-1.5 mol/L in parallel, wherein the flow rate of the nickel-copper-manganese mixed salt solution is 2-10L/h in the parallel flow adding process; the flow rate of the precipitant solution is 2-8L/h; the flow rate of the complexing agent solution is 1-3L/h, and the coprecipitation reaction is carried out for 40-120 h at the stirring speed of 230-420 rpm and the reaction temperature of 30-70 ℃ in the environment with the pH value of 7.5-9.5, so as to obtain the nickel-copper-manganese mixed salt solution;
wherein the precipitant solution comprises sodium carbonate solution and/or sodium bicarbonate solution, and the complexing agent solution comprises sodium citrate solution.
In a second aspect, the present invention provides a sodium ion positive electrode precursor material, the sodium ionThe sub-positive electrode precursor material is prepared by the preparation method according to the first aspect, and the chemical formula of the sodium ion positive electrode precursor material is Mn 1-x- y Ni x Cu y CO 3 The method comprises the steps of carrying out a first treatment on the surface of the 0.1.ltoreq.x.ltoreq.0.4, 0 < y.ltoreq.0.2, for example, x may be 0.1, 0.2, 0.3 or 0.4 etc., y may be 0.01, 0.05, 0.1, 0.15 or 0.2 etc.
In a third aspect, the invention provides a sodium ion positive electrode material, which is obtained by mixing and sintering a sodium ion positive electrode precursor material and a sodium source according to the second aspect.
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, a carbonate system is adopted for coprecipitation reaction, and a special sodium citrate complexing agent, a precipitant and a complexing agent are combined to perform synergistic effect, so that the problem of copper phase separation in the coprecipitation reaction process under a nickel-copper-manganese system is solved, the sphericity and consistency of a precursor material are improved, and the specific capacity and the cycling stability of a positive electrode material are improved.
Drawings
Fig. 1 is an SEM image of the sodium ion positive electrode precursor material provided in example 1.
Fig. 2 is an SEM image of the sodium ion positive electrode precursor material provided in comparative example 2.
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
This example provides a homogeneously precipitated sodium ion positive electrode precursor material of the formula Mn 0.7 Ni 0.2 Cu 0.1 CO 3 。
The preparation method of the precursor material comprises the following steps:
step 1, dissolving manganese sulfate, nickel sulfate and copper sulfate crystals in pure water, preparing a solution A with the total metal molar concentration of 1mol/L according to the molar ratio Mn: ni: cu=0.7:0.2:0.1, dissolving sodium carbonate in the pure water to prepare a sodium carbonate solution with the molar concentration of 1mol/L, and dissolving sodium citrate in the pure water to prepare a sodium citrate solution with the molar concentration of 0.7 mol/L;
step 2, adding the solution A, the sodium carbonate solution and the sodium citrate solution into a reaction kettle through a metering pump, simultaneously introducing nitrogen with the purity of 99.9% into the reaction kettle, stirring materials in the reaction kettle through a stirring paddle at the stirring speed of 350rpm, wherein the flow rate of the solution A is 6L/h, the flow rate of the sodium carbonate solution is 5L/h, the pH=8.5 of a reaction system is controlled, the flow rate of the sodium citrate solution is 2L/h, and the reaction temperature is 50 ℃ and the reaction time is 80h;
step 3, heating and drying after filter pressing, wherein the drying temperature is 100 ℃ and the drying time is 12 hours to obtain the Mn compound with the chemical formula 0.7 Ni 0.2 Cu 0.1 CO 3 A precursor of a manganese nickel copper sodium ion battery anode material.
Example 2
This example provides a homogeneously precipitated sodium ion positive electrode precursor material of the formula Mn 0.7 Ni 0.2 Cu 0.1 CO 3 。
The preparation method of the precursor material comprises the following steps:
step 1, dissolving manganese sulfate, nickel sulfate and copper sulfate crystals in pure water, preparing a solution A with the total metal molar concentration of 2mol/L according to the molar ratio Mn: ni: cu=0.7:0.2:0.1, dissolving sodium carbonate in the pure water to prepare a sodium carbonate solution with the molar concentration of 2mol/L, and dissolving sodium citrate in the pure water to prepare a sodium citrate solution with the molar concentration of 1.5mol/L;
step 2, adding the solution A, the sodium carbonate solution and the sodium citrate solution into a reaction kettle through a metering pump, simultaneously introducing nitrogen with the purity of 99.9% into the reaction kettle, stirring materials in the reaction kettle through a stirring paddle at the stirring speed of 420rpm, wherein the flow rate of the solution A is 2L/h, the flow rate of the sodium carbonate solution is 2L/h, the pH=9.5 of a reaction system is controlled, the flow rate of the sodium citrate solution is 1L/h, and the reaction temperature is 70 ℃ for 120h;
step 3, heating and drying after filter pressing, wherein the drying temperature is 100 ℃ and the drying time is 12 hours to obtain the Mn compound with the chemical formula 0.7 Ni 0.2 Cu 0.1 CO 3 A precursor of a manganese nickel copper sodium ion battery anode material.
Example 3
This example provides a homogeneously precipitated sodium ion positive electrode precursor material of the formula Mn 0.7 Ni 0.2 Cu 0.1 CO 3 。
The preparation method of the precursor material comprises the following steps:
step 1, dissolving manganese sulfate, nickel sulfate and copper sulfate crystals in pure water, preparing a solution A with the total metal molar concentration of 0.5mol/L according to the molar ratio Mn: ni: cu=0.7:0.2:0.1, dissolving sodium carbonate in the pure water to prepare a sodium carbonate solution with the molar concentration of 0.5mol/L, and dissolving sodium citrate in the pure water to prepare a sodium citrate solution with the molar concentration of 0.25 mol/L;
step 2, adding the solution A, the sodium carbonate solution and the sodium citrate solution into a reaction kettle through a metering pump, simultaneously introducing nitrogen with the purity of 99.9% into the reaction kettle, stirring materials in the reaction kettle through a stirring paddle at the stirring speed of 250rpm, wherein the flow rate of the solution A is 10L/h, the flow rate of the sodium carbonate solution is 8L/h, the pH=7.5 of a reaction system is controlled, the flow rate of the sodium citrate solution is 3L/h, and the reaction temperature is 30 ℃ for 40h;
step 3, heating and drying after filter pressing, wherein the drying temperature is 100 ℃ and the drying time is 12 hours to obtain the Mn compound with the chemical formula 0.7 Ni 0.2 Cu 0.1 CO 3 A precursor of a manganese nickel copper sodium ion battery anode material.
Example 4
The difference between this example and example 1 is that in this example the precipitant is sodium bicarbonate and the precursor material has the formula Mn 0.65 Ni 0.15 Cu 0.2 CO 3 。
In the preparation method, the molar ratio of transition metal is adaptively adjusted.
The remaining preparation methods and parameters were consistent with example 1.
Example 5
The difference between this example and example 1 is that the molar concentration of the sodium carbonate solution in step 1 of this example was 2.5mol/L.
The remaining preparation methods and parameters were consistent with example 1.
Example 6
The difference between this example and example 1 is that the total molar concentration of metal in solution A in step 1 of this example is 0.3mol/L.
Example 7
The difference between this example and example 1 is that the flow rate of the sodium citrate solution in step 2 of this example was 4L/h.
The remaining preparation methods and parameters were consistent with example 1.
Example 8
The difference between this example and example 1 is that the flow rate of the sodium carbonate solution in step 2 of this example was 1.0L/h.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The comparative example provides a sodium ion precursor positive electrode material under a hydroxide system, and the preparation method comprises the following steps:
step 1, dissolving manganese sulfate, nickel sulfate and copper sulfate crystals in pure water, preparing a solution A with the total metal molar concentration of 1mol/L according to the molar ratio Mn: ni: cu=0.7:0.2:0.1, dissolving sodium hydroxide in the pure water to prepare a sodium hydroxide solution with the molar concentration of 1mol/L, and preparing an ammonia water solution with the molar concentration of 0.7 mol/L;
step 2, adding the solution A, the sodium hydroxide solution and the ammonia water solution into a reaction kettle through a metering pump, simultaneously introducing nitrogen with the purity of 99.9 percent into the reaction kettle, stirring materials in the reaction kettle through a stirring paddle at the stirring speed of 350rpm, wherein the flow rate of the solution A is 6L/h, the flow rate of the sodium hydroxide solution is 5L/h, the pH=10 of a reaction system is controlled, the flow rate of the ammonia water solution is 1L/h, the reaction temperature is 50 ℃, and the reaction time is 80h;
step 3, heating and drying after filter pressing, wherein the drying temperature is 100 ℃ and the drying time is 12 hoursCan obtain the chemical molecular formula Mn 0.7 Ni 0.2 Cu 0.1 (OH) 2 A precursor of a manganese nickel copper sodium ion battery anode material.
Comparative example 2
The difference between this comparative example and example 1 is that the complexing agent solution in this comparative example is an aqueous ammonia solution.
The remaining preparation methods and parameters were consistent with example 1.
And mixing the sodium ion precursor materials sodium carbonate provided in the examples 1-8 and the comparative examples 1-2, sintering at 1000 ℃ for 12 hours, and crushing the obtained materials to obtain the sodium ion oxide positive electrode material.
Fig. 1 shows an SEM image of the sodium ion positive electrode precursor material provided in example 1, fig. 2 shows an SEM image of the sodium ion positive electrode precursor material provided in comparative example 2, and it can be seen from the comparison of fig. 1 and fig. 2 that the sodium ion precursor material obtained by the preparation method provided by the invention has a more compact structure and higher tap density, which indicates that the problem caused by copper phase separation is overcome, while the product in comparative example 2 has a loose structure, loose particles and nonuniform morphology, which indicates that the serious problem of copper phase separation occurs.
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 1-8 and comparative examples 1-2 were subjected to electrochemical performance tests under the conditions of a charge-discharge voltage of 2.0 to 4.0V, the first cycle was tested according to 0.1C/0.1C charge-discharge test, and the cycle stability was expressed as a percentage of the 50 th cycle discharge capacity divided by the first cycle discharge capacity, followed by 50 cycles at 0.5C/1C. The test results are shown in Table 1.
TABLE 1
| First discharge capacity (mAh/g) | Circulation stability | |
| Example 1 | 142.8 | 95.34％ |
| Example 2 | 141.3 | 94.26％ |
| Example 3 | 140.2 | 94.67％ |
| Example 4 | 137.9 | 93.98％ |
| Example 5 | 129.4 | 87.65％ |
| Example 6 | 126.4 | 89.42％ |
| Example 7 | 130.5 | 89.51％ |
| Example 8 | 131.7 | 88.92％ |
| Comparative example 1 | 115.6 | 67.68％ |
| Comparative example 2 | 110.3 | 70.39％ |
As can be seen from the data of examples 1 and 5-8, in the present invention, the uniform precipitation of Ni, cu and Mn elements can be achieved by synergistically controlling the molar concentration and flow rate of metal ions, precipitant solution and complexing agent solution in the nickel-copper-manganese mixed sulfate solution, and if either one of them is too large or too small, side reactions occur, resulting in the formation of inactive by-products.
As can be seen from the data results of the example 1 and the comparative examples 1-2, the precipitant and the complexing agent are cooperated, so that the homogeneous precipitation of copper in the nickel-copper-manganese system can be realized, the generation of Cu phase separation is avoided, and the precursor products which are formed by uniform precipitation and no phase separation can not be obtained by the cooperation of other systems.
In conclusion, the invention adopts a carbonate system to carry out coprecipitation reaction, combines the synergistic effect of a special sodium citrate complexing agent, a precipitant and a complexing agent, solves the problem of copper phase separation in the coprecipitation reaction process under a nickel-copper-manganese system, improves the sphericity and consistency of a precursor material, and improves the specific capacity and the cycling stability of a positive electrode material.
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. A method for preparing a sodium ion positive electrode precursor material, which is characterized by comprising the following steps:
adding a nickel-copper-manganese mixed salt solution, a precipitator solution and a complexing agent solution in parallel, and carrying out coprecipitation reaction in a protective atmosphere to obtain the nickel-copper-manganese mixed salt solution;
wherein the precipitant solution comprises a carbonate system solution and the complexing agent solution comprises a sodium citrate solution.
2. The method for preparing a sodium ion positive electrode precursor material according to claim 1, wherein the total molar concentration of metal ions in the nickel-copper-manganese mixed salt solution is 0.5-2 mol/L;
preferably, the molar concentration of the precipitant solution is 0.5-2 mol/L;
preferably, the molar concentration of the complexing agent solution is 0.25-1.5 mol/L;
preferably, the carbonate system solution comprises a sodium carbonate solution and/or a sodium bicarbonate solution.
3. The method for preparing a sodium ion positive electrode precursor material according to claim 1 or 2, wherein the flow rate of the nickel-copper-manganese mixed salt solution is 2-10L/h.
4. The method for preparing a sodium ion positive electrode precursor material according to any one of claims 1 to 3, wherein the flow rate of the precipitant solution is 2 to 8L/h;
preferably, the flow rate of the complexing agent solution is 1-3L/h.
5. The method for preparing a sodium ion positive electrode precursor material according to any one of claims 1 to 4, wherein the pH value during the coprecipitation reaction is 7.5 to 9.5;
preferably, the stirring speed of the coprecipitation reaction is 230-420 rpm.
6. The method for producing a sodium ion positive electrode precursor material according to any one of claims 1 to 5, wherein the temperature of the coprecipitation reaction is 30 to 70 ℃;
preferably, the time of the coprecipitation reaction is 40 to 120 hours.
7. The method for producing a sodium ion positive electrode precursor material according to any one of claims 1 to 6, comprising the steps of:
adding nickel-copper-manganese mixed salt solution with the total molar concentration of metal ions of 0.5-2 mol/L, precipitant solution with the molar concentration of 0.5-2 mol/L and complexing agent solution with the molar concentration of 0.25-1.5 mol/L in parallel, wherein the flow rate of the nickel-copper-manganese mixed salt solution is 2-10L/h in the parallel flow adding process; the flow rate of the precipitant solution is 2-8L/h; the flow rate of the complexing agent solution is 1-3L/h, and the coprecipitation reaction is carried out for 40-120 h at the stirring speed of 230-420 rpm and the reaction temperature of 30-70 ℃ in the environment with the pH value of 7.5-9.5, so as to obtain the nickel-copper-manganese mixed salt solution;
wherein the precipitant solution comprises sodium carbonate solution and/or sodium bicarbonate solution, and the complexing agent solution comprises sodium citrate solution.
8. A sodium ion positive electrode precursor material, wherein the sodium ion positive electrode precursor material is prepared by the preparation method according to any one of claims 1 to 7, and has a chemical formula of Mn 1-x- y Ni x Cu y CO 3 ；0.1≤x≤0.4、0＜y≤0.2。
9. A sodium ion positive electrode material, which is obtained by mixing and sintering the sodium ion positive electrode precursor material according to claim 8 and a sodium source.
10. A sodium ion battery comprising the sodium ion positive electrode material of claim 9.
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