CN114914425B - Inorganic high-molecular water purifying agent coated positive electrode material and preparation method and application thereof - Google Patents
Inorganic high-molecular water purifying agent coated positive electrode material and preparation method and application thereof Download PDFInfo
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- CN114914425B CN114914425B CN202210591877.7A CN202210591877A CN114914425B CN 114914425 B CN114914425 B CN 114914425B CN 202210591877 A CN202210591877 A CN 202210591877A CN 114914425 B CN114914425 B CN 114914425B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 62
- 239000012629 purifying agent Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- -1 titanium aluminum magnesium Chemical compound 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 5
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 5
- 229910015694 LiNi0.85Co0.1Al0.05O2 Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- JEGSVFUREJDEAP-UHFFFAOYSA-L aluminum;titanium(4+);sulfate Chemical compound [Al+3].[Ti+4].[O-]S([O-])(=O)=O JEGSVFUREJDEAP-UHFFFAOYSA-L 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 38
- 238000005406 washing Methods 0.000 abstract description 11
- 239000011247 coating layer Substances 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 9
- 150000004706 metal oxides Chemical class 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012876 topography Methods 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000005253 cladding Methods 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 229920000592 inorganic polymer Polymers 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229940103272 aluminum potassium sulfate Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 2
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an inorganic high polymer water purifying agent coated positive electrode material, and a preparation method and application thereof, wherein the preparation method of the inorganic high polymer water purifying agent coated positive electrode material comprises the following steps: mixing an inorganic composite high-molecular water purifying agent, a positive electrode base material and a solvent, and drying and sintering to obtain the positive electrode material; the inorganic composite polymer water purifying agent comprises aluminum element and titanium element. The coating layer of the positive electrode material formed by the method is uniform and compact, so that the corrosion of electrolyte is effectively avoided, and side reactions are greatly reduced; the method combines the water washing and coating processes, shortens the process flow, greatly reduces the production cost, and simultaneously obtains the metal oxide co-coated anode material with excellent cycle performance and safety performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an inorganic high-molecular water purifying agent coated positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries are products of the 80 th century of the 20 th century, and because of the advantages of performance and technology, the technology of lithium batteries is mature over decades, and the lithium ion batteries are successfully commercialized on a large scale, and are applied to various aspects of our life, and are specifically classified into lithium power batteries, lithium consumer batteries and lithium energy storage batteries according to use scenes and energy sizes, and lithium cobalt oxide materials (pd=4.1 g/cc) with higher compaction density are preferably selected as high-end products of the lithium consumer batteries, and the volume energy density of the batteries made of the materials of the type is high. The lithium energy storage battery is a lithium iron phosphate battery with good cycle performance and low energy density, the energy storage power station has low requirements on the field, and the lithium iron phosphate battery with low volume energy density is used. In recent years, as a lithium power battery at a main application end of the lithium battery, a ternary material with high energy density, slightly poor cycle and safety performance, but balanced comprehensive indexes is used on a large scale due to the requirement of the endurance mileage.
It is generally considered that the cyclic attenuation of the ternary material is caused by the phase change after the cycle, lithium ions consumed by lithium-nickel mixed discharge and contact side reaction between the surface and the electrolyte are treated by surface coating, and in order to improve the long-term performance and safety performance of the ternary material, the treatment process generally adopted in the industry is classified into dry coating and wet coating according to the difference of coating processes, and inorganic coating and organic coating according to the difference of the types of coating materials, and coating equipment comprises a high-speed kneader, a high-speed mixer, a spray dryer and the like. Whether a uniform coating layer is formed or not is a key for judging the coating quality.
After primary sintering, the ternary material is subjected to a water washing procedure after primary sintering to reduce the surface residual alkali, so that the surface residual alkali LiOH and Li are caused 2 CO 3 、Li 2 O and the like are dissolved in water, filtered and then flows out along with the filtrate, and alkaline substances containing Li are separated from ternary materials, so that residual alkali on the surface of the ternary materials is reduced.
CN112758991a discloses a preparation method of a ternary positive electrode material precursor with a core-shell structure, which comprises the following steps: (1) Preparing a metal salt solution, a precipitator solution, a complexing agent solution and an amphoteric polymer flocculant solution; (2) Adding water, complexing agent solution and precipitant solution into a reaction kettle to prepare reaction kettle bottom solution; (3) Adding a metal salt solution, a precipitator solution and a complexing agent solution into the bottom solution of the reaction kettle, performing coprecipitation reaction, starting to introduce an amphoteric polymer flocculant solution when the particle size in the reaction kettle grows to be smaller than the target particle size of 2-3 mu m, then continuing to perform reaction until the average particle size of the particles grows to the target particle size, and stopping feeding. The method disclosed by the invention utilizes the polymeric flocculant to form a reticular structure on the outer layer of the precursor particles, thereby enhancing the structural strength of the precursor particles, avoiding the occurrence of ball cracking caused by collision among the particles in the later stage of precursor reaction, and further ensuring the circularity, stability and safety of the precursor particles.
The general flow of the large-scale production of the ternary material is as follows: the surface is stably coated by sintering, washing, coating inorganic matters by a dry method and sintering again. The water washing is used for removing residual alkali on the surface of the ternary material, the dry coating such as Al, ti, mg, zr and the like is used for sintering again to form physical isolation, reduce side reactions of electrolyte and improve safety performance and cycle stability, but even the dry coating is carried out by using a nano-level coating, the coating still does not complete, and the two reasons are that firstly, the coating Al, ti, mg and Zr are in nano states, but the nano materials have common characteristics of easy agglomeration, and the particle raw materials are easy to agglomerate after mutually contacting, so that the nano coating is not easy to disperse in the coating process; and secondly, the ternary material coating equipment is powder dispersing or kneading equipment, the microscopic mixing effect is poor, the local coating effect is poor, and the upper limit of the mixing capability is low, so that the surface of the ternary material powder which is still fresh and not coated after being coated and sintered is exposed in electrolyte, the surface is not completely coated by the dry coating, and the side reaction problem of the ternary material and the electrolyte and the surface phase change problem caused by the side reaction of the electrolyte still cannot be solved.
In view of the above, it is important to develop a method capable of reducing side reactions between the positive electrode material and the electrolyte and ensuring the positive electrode material to exert excellent electrochemical properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an inorganic high-molecular water purifying agent coated positive electrode material, a preparation method and application thereof, wherein a coating layer of the positive electrode material formed by the method is uniform and compact, thereby effectively avoiding corrosion of electrolyte and greatly reducing side reaction; the method combines the water washing and coating processes, shortens the process flow, greatly reduces the production cost, and simultaneously obtains the metal oxide co-coated anode material with excellent cycle performance and safety performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an inorganic polymer water purifying agent coated positive electrode material, where the method for preparing the inorganic polymer water purifying agent coated positive electrode material includes the following steps:
mixing an inorganic composite high-molecular water purifying agent, a positive electrode base material and a solvent, and drying and sintering to obtain the positive electrode material;
the inorganic composite polymer water purifying agent comprises aluminum element and titanium element.
According to the invention, a ternary material water washing process is utilized, under the premise of not adding an additional complexing agent and a precipitant (organic impurities are introduced, carbon residues are caused after sintering), a sewage treatment agent inorganic composite polymeric flocculant is directly used, the super-strong adsorption and bridging effects of the inorganic composite polymeric flocculant are utilized, metal atoms are hydrolyzed, flocculent colloid exists, after the ternary material is added into water, metal ions are further promoted to hydrolyze under the effects of a ternary material suspension and a high pH value to form colloid, the colloid is uniformly adsorbed on the surface of the ternary material to form a complete coating layer, and then the coating layer which is co-coated by different metal oxides is obtained after re-sintering.
The method disclosed by the invention does not need to adjust the pH value, only carries out one-time sintering, uses the ternary material coated by the inorganic composite high-molecular water purifying agent, has a clearly visible surface coating layer, is in a sheet-like complete coating shape, and basically has no surface exposure of the fresh ternary material.
The anode material coated by the uniform metal oxide prepared by the method has the advantages that the coating layer is uniform and compact, the corrosion of electrolyte is effectively avoided, the side reaction is greatly reduced, the water washing and coating processes are combined, the process flow is shortened, the production cost is greatly reduced, and the metal oxide co-coated ternary material with excellent cycle performance and safety performance is obtained.
Preferably, the inorganic composite polymer water purifying agent comprises phosphorus sulfur aluminum titanium and/or silicon sulfur aluminum titanium magnesium.
In the invention, the polyphosphate sulfur aluminum titanium refers to [ Ti ] 0.25-0.75x Al x (PSO 6 )]n；
The polysilicosulfa aluminum titanium magnesium refers to [ Mg ] 1-2y-1.5x Ti y Al x (SiSO 6 )]n。
Preferably, in the inorganic composite polymer water purifying agent, the mass percentage of aluminum is 10% -20% (e.g. 12%, 14%, 16%, 18%, etc.), the mass percentage of titanium is 10% -25% (e.g. 12%, 14%, 16%, 18%, 20%, 22%, 24%, etc.), and the mass percentage of Mg is 1% -15% (e.g. 2%, 4%, 6%, 8%, 10%, 12%, 14%, etc.).
In the invention, the phosphorus sulfur aluminum titanium [ Ti ] 0.25-0.75x Al x (PSO 6 )]n adjusts the mass percent of aluminum and titanium within a specific range, because: excessive aluminum duty cycle can lead to increased interfacial electron conduction impedance; too low a duty cycle may result in reduced coating effect; the excessive titanium ratio can lead to the increase of interface ion conduction impedance; too low a ratio may result in a reduced coating effect.
Preferably, the inorganic composite polymer water purifying agent is 0.1 to 5 parts by mass, for example, 0.2 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, etc., based on 100 parts by mass of the total positive electrode substrate.
In the invention, the mass ratio of the positive electrode base material to the inorganic composite high polymer water purifying agent is controlled in a specific range, and the reason is that: the inorganic composite high molecular water purifying agent has an excessively heavy duty ratio, and can cause the increase of ionic and electronic impedance; too low a ratio may result in a reduced coating effect.
Preferably, the inorganic composite polymer water purifying agent is dissolved in a solvent to form a water purifying agent solution, and then the water purifying agent solution is mixed with the positive electrode base material.
Preferably, the solvent comprises water.
Preferably, in the water purifying agent solution, the mass ratio of the inorganic composite polymer water purifying agent to the solvent is (0.1-10): 100, wherein 0.1-10 can be 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 and the like.
Preferably, the positive electrode base material includes LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNiO 2 Or LiNi 0.85 Co 0.1 Al 0.05 O 2 Any one or a combination of at least two, wherein a typical but non-limiting combination includes: liNi 0.8 Co 0.1 Mn 0.1 O 2 And LiNiO 2 Is LiNiO 2 And LiNi 0.85 Co 0.1 Al 0.05 O 2 Is LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNiO 2 Or LiNi 0.85 Co 0.1 Al 0.05 O 2 Combinations of (a) and the like.
Preferably, the drying includes suction filtration and vacuum drying.
Preferably, the sintering temperature is 400-800 ℃, e.g. 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, etc.
Preferably, the sintering time is 1-10 hours, such as 2 hours, 4 hours, 6 hours, 8 hours, etc.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Mixing and dissolving an inorganic composite high molecular water purifying agent and a solvent according to the mass ratio of (0.1-10): 100 to obtain a water purifying agent solution;
(2) Mixing the water purifying agent solution with the positive electrode base material, and adjusting the mass ratio of the inorganic composite polymer water purifying agent to the positive electrode base material to be (0.1-5) 100;
(3) And (3) carrying out suction filtration and vacuum drying on the mixed raw material in the step (2), and sintering at 400-800 ℃ for 1-10h to obtain the positive electrode material.
In a second aspect, the present invention provides a positive electrode material prepared by the method of the first aspect.
In a third aspect, the invention provides a positive electrode plate, which comprises the inorganic polymer water purifying agent coated positive electrode material, a conductive agent and an adhesive in the second aspect.
In a fourth aspect, the present invention provides a battery comprising the positive electrode tab of the third aspect, an electrolyte, a separator, and a negative electrode tab.
Compared with the prior art, the invention has the following beneficial effects:
(1) The anode material coated by the uniform metal oxide prepared by the method has the advantages that the coating layer is uniform and compact, the corrosion of electrolyte is effectively avoided, the side reaction is greatly reduced, the water washing and coating processes are combined, the process flow is shortened, the production cost is greatly reduced, and the metal oxide co-coated ternary material with excellent cycle performance and safety performance is obtained.
(2) The capacity retention rate of the battery formed by the positive electrode material is more than 95.73% after the battery is cycled for 200 times.
Drawings
FIG. 1 is a graph of the cycle performance of the positive electrode materials described in examples 1-3 and comparative examples 1-4;
FIG. 2 is a surface topography of the positive electrode material of example 1;
FIG. 3 is a surface topography of the positive electrode material of comparative example 1;
FIG. 4 is a surface topography of the positive electrode material of comparative example 2;
FIG. 5 is a surface topography of the positive electrode material of comparative example 3;
FIG. 6 is a surface topography of the positive electrode material of comparative example 4;
fig. 7 is a surface topography of an uncoated positive electrode material.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. 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 positive electrode material, which is prepared by a method comprising the following steps:
1) 10g of inorganic composite polymer phosphorus sulfur aluminum titanium water purifying agent (purchased from Zibodostar water purifying agent Limited liability company) is weighed, the Al content is 11.5 percent, and the Ti content is 20.4 percent;
2) Dissolving in 1000g of water, and stirring for 10 minutes;
3) After the inorganic composite polymer is completely hydrolyzed, 2000g of uncoated LiNi is added 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material is stirred for 10 minutes;
4) Suction filtering, taking a lower filter cake, and vacuum drying;
5) Sintering for 6h in 600 ℃ air atmosphere to obtain Al 2 O 3 、TiO 2 And uniformly co-cladding the ternary material, namely the positive electrode material.
Example 2
The embodiment provides a positive electrode material, which is prepared by a method comprising the following steps:
1) 10g of inorganic composite polymer polysilico-aluminum-titanium-magnesium water purifying agent (purchased from Zibo star water purifying agent Limited liability company) is weighed, the Al content is 14.9%, the Ti content is 13.2% and the Mg content is 6.7%;
2) Dissolving in 1000g of water, stirring for 10 minutes,
3) After the inorganic composite polymer is completely hydrolyzed, 2000g of uncoated LiNi is added 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material was stirred for 10 minutes,
4) Filtering, taking out the lower filter cake, vacuum drying,
5) Sintering for 6h in 600 ℃ air atmosphere to obtain Al 2 O 3 、TiO 2 And uniformly co-coating the ternary material with MgO to obtain the positive electrode material.
Example 3
The embodiment provides a positive electrode material, which is prepared by a method comprising the following steps:
1) 10g of inorganic composite polymer phosphorus sulfur aluminum titanium water purifying agent (purchased from Zibodostar water purifying agent Co., ltd.) is weighed, the Al content is 15.34 percent, and the Ti content is 13.59 percent;
2) Dissolving in 1000g of water, and stirring for 10 minutes;
3) After the inorganic composite polymer is completely hydrolyzed, 2000g of uncoated LiNi is added 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material is stirred for 10 minutes;
4) Suction filtering, taking a lower filter cake, and vacuum drying;
5) Sintering for 6h in 600 ℃ air atmosphere to obtain Al 2 O 3 、TiO 2 And uniformly co-cladding the ternary material, namely the positive electrode material.
Comparative example 1
This comparative example provides a positive electrode material prepared by a method comprising the steps of:
1) Weighing 1000g of water, and stirring for 10 minutes;
2) 2000g of uncoated LiNi was added 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material is stirred for 10 minutes;
3) Suction filtering, taking a lower filter cake, and vacuum drying;
4) 2000g of dried ternary material, 2.17g of nano alumina and 3.4g of nano titanium oxide are taken, added into a high-speed mixer and mixed for 30 minutes at 1000 revolutions;
5) Sintering for 6h in 600 ℃ air atmosphere to obtain Al 2 O 3 、TiO 2 And (3) coating the ternary material by a dry method, namely the positive electrode material.
Comparative example 2
This comparative example provides a positive electrode material prepared by a method comprising the steps of:
1) Weighing 1000g of water, and stirring for 10 minutes;
2) 2000g of uncoated LiNi was added 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material is stirred for 10 minutes;
3) Suction filtering, taking a lower filter cake, and vacuum drying;
4) 2000g of dried ternary material, 2.81g of nano alumina, 2.20g of nano titanium oxide and 1.11g of nano magnesium oxide are taken and added into a high-speed mixer to be mixed for 30 minutes at 1000 revolutions;
5) Sintering for 6h in 600 ℃ air atmosphere to obtain Al 2 O 3 、TiO 2 The MgO dry method co-cladding ternary material isThe positive electrode material.
Comparative example 3
This comparative example provides a positive electrode material prepared by a method comprising the steps of:
1) 10g of inorganic composite polymer polyphosphoric acid (purchased from Miou, tianjin, denmark) is weighed and dissolved in 200g of water, and stirred for 10 minutes to obtain a solution A;
10.95g of aluminum potassium sulfate, 10.5 g of Al content, 10.25g of titanium sulfate and 19.9% of Ti content are dissolved in 200g of water and stirred for 10 minutes to obtain a solution B;
2) 600g of water was weighed and 2000g of uncoated LiNi was added 0.8 Co 0.1 Mn 0.1 O 2 Adding the positive electrode material, adding the A and the B at the same time, and stirring for 10 minutes;
4) Suction filtering, taking a lower filter cake, and vacuum drying;
5) Sintering for 6h in 600 ℃ air atmosphere to obtain Al 2 O 3 、TiO 2 And uniformly co-cladding the ternary material, namely the positive electrode material.
Comparative example 4
This comparative example provides a positive electrode material prepared by a method comprising the steps of:
1) Weighing 20.20g of aluminum potassium sulfate dodecahydrate water purifying agent, wherein the Al content is 5.69%;
2) Dissolving in 1000g of water, and stirring for 10 minutes;
3) After the inorganic water purifying agent is completely hydrolyzed, 2000g of uncoated LiNi is added 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material is stirred for 10 minutes;
4) Suction filtering, taking a lower filter cake, and vacuum drying;
5) Sintering for 6h in 600 ℃ air atmosphere to obtain Al 2 O 3 And coating the ternary material, namely the positive electrode material.
Performance testing
The positive electrode materials described in examples 1 to 3 and comparative examples 1 to 4 were subjected to the following tests:
(1) Surface morphology: observing the surface morphology of the positive electrode material by using a scanning electron microscope;
the positive electrode materials described in examples 1-3 and comparative examples 1-4 were assembled into button cells for the following tests:
and (3) battery assembly: the positive electrode material, the conductive agent (SP) and the polyvinylidene fluoride are weighed according to the mass ratio of 80:10:10, a certain amount of N-methyl pyrrolidone is added after the materials are uniformly mixed, the uniformly mixed slurry is coated on a current collector by a scraper, the current collector is dried for 90min at 120 ℃, a roller is used for rolling, then a slicer is used for slicing, and qualified pole pieces are selected. And then assembling the pole piece, the electrolyte, the diaphragm, the lithium piece and the battery shell into a 2032 type button battery in a glove box filled with argon.
Electrochemical performance test: the Wuhan blue electric tester, 25 ℃, the theoretical capacity is calculated according to 180mAh/g, the first two rounds of charging use 0.1C constant current to charge to 4.25V,4.25V constant voltage discharge, cut-off current is 0.02C, then use 1C constant current to charge to 4.25V,4.25V constant voltage discharge, electric cut-off current is 0.02C, and the cycle is 50 times.
The test results are summarized in table 1 and in fig. 1-7.
TABLE 1
| Capacity retention after 200 cycles (%) | |
| Example 1 | 97.90 |
| Example 2 | 97.56 |
| Example 3 | 95.73 |
| Comparative example 1 | 91.09 |
| Comparative example 2 | 91.56 |
| Comparative example 3 | 85.89 |
| Comparative example 4 | 89.85 |
As can be seen from the analysis of the data in table 1, the capacity retention rate of the battery formed of the positive electrode material according to the present invention was 95.73% or more after 200 cycles, and as shown in fig. 1, the capacity of the battery formed of the positive electrode material according to the present invention was maintained within a stable range as the number of cycles was increased. The positive electrode material formed by the method has excellent electrochemical performance.
As can be seen from an analysis of FIGS. 2 to 7, FIG. 7 shows an uncoated positive electrode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 In the invention, as shown in the figure 2, the apparent morphology of the invention is as shown in the example 1, and the inorganic composite high-molecular water purifying agent is used for carrying out surface uniform co-cladding in the water washing process, and after the ternary material is sintered, the metal cladding layer is uniformly clad on the surface of the material to form a complete mechanical protection layer, so that the negative reaction with electrolyte in the battery cycle process is eliminated, the crystal structure is stabilized, and the cycle phase change is reduced.
In comparative examples 1-2, dry coating of LiNi was employed 0.8 Co 0.1 Mn 0.1 O 2 The surface topography is shown in fig. 3 and 4, respectively; in comparative example 3, inorganic composite polymer polyphosphoric acid is adopted to be matched with aluminum potassium sulfate and titanium sulfate for wet coating, the surface morphology is shown in figure 5, and the addition of polyphosphoric acid, washing with water is acidic to influence the hydrolysis of Al ions, so that a coating layer cannot be formed; at the position ofIn comparative example 4, the inorganic potassium aluminum sulfate dodecahydrate water purifying agent was used for wet coating, and the surface morphology is shown in fig. 6, and since the inorganic water purifying agent is hydrolyzed by Al ions alone, the coating layer is not complete, and the coating effect is reduced compared with the inorganic polymer composite water purifying agent.
In conclusion, the method disclosed by the invention does not need to adjust the pH value, only performs one-time sintering, uses the ternary material coated by the inorganic composite high-molecular water purifying agent, has a clearly visible surface coating layer, is in a sheet-like complete coating shape, and basically has no surface exposure of the fresh ternary material. In the prior art, under the same conditions, the coating is in a punctiform coating, most of the surface of the positive electrode material is still exposed outside, and the battery is manufactured by using the material.
In conclusion, the anode material coated by the uniform metal oxide prepared by the method has the advantages that the coating layer is uniform and compact, the corrosion of electrolyte is effectively avoided, the side reaction is greatly reduced, the water washing and coating processes are combined, the process flow is shortened, the production cost is greatly reduced, and meanwhile, the metal oxide co-coated ternary material with excellent cycle performance and safety performance is obtained.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (13)
1. The preparation method of the inorganic high polymer water purifying agent coated positive electrode material is characterized by comprising the following steps of:
mixing an inorganic composite high-molecular water purifying agent, a positive electrode base material and a solvent, and drying and sintering to obtain the positive electrode material;
the inorganic composite polymer water purifying agent comprises aluminum element and titanium element;
based on 100 parts of the total mass of the positive electrode base material, the inorganic composite polymer water purifying agent is 0.1-5 parts by mass;
the sintering temperature is 400-800 ℃.
2. The preparation method according to claim 1, wherein the inorganic composite polymer water purifying agent comprises polyphosphoric titanium aluminum sulfate and/or polysilicium titanium aluminum magnesium.
3. The preparation method of claim 1, wherein in the inorganic composite polymer water purifying agent, the mass percentage of aluminum is 10% -20%, and the mass percentage of titanium is 10% -25%.
4. The method according to claim 1, wherein the inorganic composite polymer water purifying agent is dissolved in a solvent to form a water purifying agent solution, and then mixed with the positive electrode substrate.
5. The method of claim 4, wherein the solvent comprises water.
6. The process according to claim 4, wherein the mass ratio of the inorganic composite polymer water purifying agent to the solvent in the water purifying agent solution is (0.1-10): 100.
7. The method of claim 1, wherein the positive electrode substrate comprises LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNiO 2 Or LiNi 0.85 Co 0.1 Al 0.05 O 2 Any one or a combination of at least two of these.
8. The method of claim 1, wherein the drying comprises suction filtration and vacuum drying.
9. The method of claim 1, wherein the sintering time is 1 to 10 hours.
10. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Mixing and dissolving an inorganic composite high molecular water purifying agent and a solvent according to the mass ratio of (0.1-10): 100 to obtain a water purifying agent solution;
(2) Mixing the water purifying agent solution with the positive electrode base material, and adjusting the mass ratio of the inorganic composite polymer water purifying agent to the positive electrode base material to be (0.1-5) 100;
(3) And (3) carrying out suction filtration and vacuum drying on the mixed raw material in the step (2), and sintering at 400-800 ℃ for 1-10h to obtain the positive electrode material.
11. An inorganic high molecular water purifying agent coated positive electrode material, which is characterized in that the positive electrode material is prepared by the method of any one of claims 1-10.
12. The positive electrode plate is characterized by comprising the inorganic high-molecular water purifying agent coated positive electrode material, a conductive agent and an adhesive according to claim 11.
13. A battery comprising the positive electrode sheet, electrolyte, separator and negative electrode sheet of claim 12.
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| CN108134069A (en) * | 2017-12-26 | 2018-06-08 | 深圳市贝特瑞纳米科技有限公司 | A kind of composite modifying method of anode material for lithium-ion batteries |
| CN108666550A (en) * | 2018-04-27 | 2018-10-16 | 成都新柯力化工科技有限公司 | A kind of preparation method of the nickelic ternary anode material of lithium battery with concentration gradient |
| WO2021068448A1 (en) * | 2019-10-10 | 2021-04-15 | 蜂巢能源科技有限公司 | Quaternary positive electrode material for lithium ion battery and preparation method therefor, and lithium ion battery |
| WO2021136243A1 (en) * | 2019-12-30 | 2021-07-08 | 北京当升材料科技股份有限公司 | Modified lithium nickel cobalt aluminate positive electrode material, preparation method therefor and application thereof |
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| CN108134069A (en) * | 2017-12-26 | 2018-06-08 | 深圳市贝特瑞纳米科技有限公司 | A kind of composite modifying method of anode material for lithium-ion batteries |
| CN108666550A (en) * | 2018-04-27 | 2018-10-16 | 成都新柯力化工科技有限公司 | A kind of preparation method of the nickelic ternary anode material of lithium battery with concentration gradient |
| WO2021068448A1 (en) * | 2019-10-10 | 2021-04-15 | 蜂巢能源科技有限公司 | Quaternary positive electrode material for lithium ion battery and preparation method therefor, and lithium ion battery |
| WO2021136243A1 (en) * | 2019-12-30 | 2021-07-08 | 北京当升材料科技股份有限公司 | Modified lithium nickel cobalt aluminate positive electrode material, preparation method therefor and application thereof |
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