CN114927658A - Device and method for modifying surface of anode material based on ion exchange membrane - Google Patents
Device and method for modifying surface of anode material based on ion exchange membrane Download PDFInfo
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- CN114927658A CN114927658A CN202210485883.4A CN202210485883A CN114927658A CN 114927658 A CN114927658 A CN 114927658A CN 202210485883 A CN202210485883 A CN 202210485883A CN 114927658 A CN114927658 A CN 114927658A
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- positive electrode
- electrode material
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- exchange membrane
- cation
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- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000010405 anode material Substances 0.000 title claims description 36
- 239000007774 positive electrode material Substances 0.000 claims abstract description 108
- 150000001450 anions Chemical class 0.000 claims abstract description 103
- 150000001768 cations Chemical class 0.000 claims abstract description 88
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 238000005341 cation exchange Methods 0.000 claims abstract description 9
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 95
- 238000000576 coating method Methods 0.000 claims description 80
- 239000011248 coating agent Substances 0.000 claims description 78
- 239000002243 precursor Substances 0.000 claims description 50
- 238000005245 sintering Methods 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 45
- 239000011259 mixed solution Substances 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 40
- 230000004048 modification Effects 0.000 claims description 38
- 238000012986 modification Methods 0.000 claims description 38
- 239000010406 cathode material Substances 0.000 claims description 34
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- 238000001556 precipitation Methods 0.000 claims description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 claims description 8
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a device and a method for modifying the surface of a positive electrode material based on an ion exchange membrane. The device for modifying the surface of the positive electrode material based on the ion exchange membrane comprises: a cation chamber containing a cation solution therein; an anion chamber containing an anion solution therein; an ion exchange membrane for physical separation of an anion chamber and a cation chamber, the ion exchange membrane comprising a cation exchange membrane and an anion exchange membrane; and the stirring system is respectively arranged at the bottom of the cation chamber and the bottom of the anion chamber or/and the flowing system is respectively communicated and connected with the cation chamber and the anion chamber.
Description
Technical Field
The invention relates to surface modification of a lithium ion anode material, in particular to a device and a method for surface modification of a lithium ion anode material, and belongs to the field of chemical energy storage batteries.
Background
The rapid development of new energy automobiles puts higher requirements on the specific capacity and the safety of the anode material used by the power battery. In the current commercialized spinel-type, olivine-type and layered-type cathode materials, the ternary layered cathode material is widely concerned due to excellent specific capacity, and although the increase of the nickel content can improve the specific capacity of the ternary cathode and reduce the cost, the cycle performance, the thermal stability and the safety of the ternary cathode material are rapidly deteriorated with the increase of the nickel content, and the practical application of the ternary cathode material is severely restricted. The root cause of the above problems is derived from the material properties of the high-nickel ternary positive electrode, including the dissolution of metal elements and Ni having strong oxidation properties in the state of charge 4+ Side reaction with electrolyte and surface reconstruction occur to generate high-impedance NiO phase and release active oxygen, which causes gas and heat generation of batteryOut of control. At present, scholars at home and abroad mainly coat the surface of the ternary material to inhibit the dissolution of transition metal and isolate high-activity Ni 4+ Direct contact with the electrolyte solves the above mentioned disadvantages.
At present, methods for coating the surface of the anode material mainly comprise a coprecipitation method, a sol-gel method, a hydrothermal method, a chemical vapor deposition method, an atomic deposition method, a solid-phase ball milling method and the like, but still have the problems of high cost, nonuniform coating and the like. The precursor salts of the sol-gel method and the hydrothermal method are expensive, and the yield is low; the chemical vapor deposition method and the atomic deposition method have long processing time, strong toxicity and complex process, and the solid phase ball milling method is difficult to obtain a uniform coating layer. The key point of uniform coating is the regulation and control of the coating layer, and the key point of the regulation and control of the coating layer is the slow deposition of the coating substance on the surface of the coated substance, and the formation of two separated phases is avoided through diffusion control. The current uniform control strategy of the coating layer mainly comprises buffer solution, slow release of precipitation, catalyst assistance, charge interaction and the like. The strategy can effectively realize the precise regulation and control of the coating layer, and can obviously improve the performance of the anode material, but has the problems of low universality, complex operation and the like. Therefore, the method which is convenient to operate and has an important significance for uniformly coating the anode material is developed.
Disclosure of Invention
Aiming at the problems, the invention provides a device and a method for modifying the surface of a positive electrode material based on an ion exchange membrane.
In a first aspect, the present invention provides an apparatus for modifying the surface of a positive electrode material based on an ion exchange membrane, comprising:
a cation chamber containing a cation solution therein;
an anion chamber containing an anion solution therein;
an ion exchange membrane for physical separation of an anion chamber and a cation chamber, the ion exchange membrane comprising a cation exchange membrane and an anion exchange membrane;
and the stirring system is respectively arranged at the bottom of the cation chamber and the bottom of the anion chamber or/and the flowing system is respectively communicated and connected with the cation chamber and the anion chamber.
According to the invention, based on the ion exchange effect of the ion exchange membrane, the surface modification is carried out on the lithium ion anode material, so that the electrochemical performance and safety of the lithium ion anode material are improved, the modification cost is reduced, and the coating uniformity is improved. The method has the advantages of convenient operation, uniform coating and easy expanded production.
Preferably, the flow system comprises:
the cation solution storage tank is communicated with the flow pump and the flow pipeline of the cation chamber and the cation solution storage tank;
an anion solution storage tank, a flow pump and a flow pipeline which are communicated with the anion chamber and the anion solution storage tank.
Preferably, stirring devices are arranged inside the cation chamber and the anion chamber, wherein the stirring devices include at least one of a magnetic stirring device, a mechanical stirring device, an ultrasonic stirring device and other stirring devices.
Preferably, the active groups in the cation exchange membrane comprise at least one of sulfonic acid groups, phosphoric acid groups, carboxylic acid groups, phenol groups \ arsenic acid groups and selenium acid groups; the active group in the anion exchange membrane comprises at least one of amino and arylamino of primary, secondary, tertiary and quaternary amines.
Preferably, the positive electrode material comprises a lithiated positive electrode material and a positive electrode precursor material;
the post lithiated positive electrode material comprises LiNi b Co c Mn 1-b-c O 2 (wherein b is more than or equal to 0 and less than or equal to 1, and c is more than or equal to 0 and less than or equal to 1); and LiNi m Co n Al 1-m-n O 2 (0≤m≤1，0≤n≤1)；
The positive electrode precursor material includes Ni (1-y-z) Co y Mn z (OH) 2 (wherein y is 0. ltoreq. y.ltoreq.1, z is 0. ltoreq. z.ltoreq.1) and Ni (1-a-d) Co a Al d (OH) 2 (wherein a is more than or equal to 0 and less than or equal to 1, and d is more than or equal to 0 and less than or equal to 1).
Preferably, the solute in the cation solution is selected from Al (NO) 3 ) 3 、Al 2 (SO 4 ) 3 、AlCl 3 、MnCl 3 、 Co(NO 3 ) 3 、Co 2 (SO 4 ) 3 、Fe(NO 3 ) 3 、Fe 2 (SO 4 ) 3 、FeCl 3 、Cr(NO 3 ) 3 、Cr 2 (SO 4 ) 3 、CrCl 3 、 Zr(NO 3 ) 4 、ZrCl 4 、Zn(NO 3 ) 3 、TiBr 4 At least one of (a).
Preferably, the solvent in the cationic solution includes at least one of distilled water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cycloethanol, acetone, cyclohexanone, glycerol and ethyl acetate.
Preferably, the concentration of the cation solution is 0.01 mol/L-10 mol/L.
Preferably, the solute in the anionic solution is selected from KOH, NaOH, LiOH, (NH) 4 ) 2 HPO 4 、NH 4 H 2 PO 4 、H 3 PO 4 、NH 3 ·H 2 At least one of KF in O, LiF and NaF.
Preferably, the solvent in the anionic solution comprises at least one of distilled water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cycloethanol, acetone, cyclohexanone, glycerol and ethyl acetate. The concentration of the anion solution is 0.01 mol/L-10 mol/L.
Preferably, the device for surface modification of the ion exchange membrane-based cathode material further comprises an external power supply connected to the cation chamber and the anion chamber.
In a second aspect, the present invention provides a method for modifying a surface of a positive electrode material, comprising:
(1) dispersing a positive electrode material in a cation solution or an anion solution in the device for modifying the surface of the positive electrode material based on the ion exchange membrane, combining the anion solution with the cation solution through a stirring system or a flowing system, and carrying out a precipitation reaction or an oxidation reduction reaction to generate a precipitate, so that a coating substance is formed on the surface of the positive electrode material or at the particle pores of the positive electrode material, and separating and drying to obtain the positive electrode material with the coating substance distributed on the surface;
(4) and carrying out heat treatment on the positive electrode material with the coating substance distributed on the surface to obtain the surface modified positive electrode material.
In the invention, the unique device structure is adopted, the ion exchange membrane is adopted to isolate the anions and the cations of the coating or filling substance, no external power supply is needed, and the anions and the cations are slowly combined to generate precipitation reaction or oxidation reduction reaction to generate precipitation, thereby obtaining the coating substance. Of course, the applied power source can also be, i.e., the concentration diffusion plus the faster migration of charged ions under the electric field. Because the process of generating the precipitate is controlled by the diffusion rate of ions in the ion exchange membrane, the supersaturation degree of the coating substance in the mixed liquid system of the anode material is always kept at a lower level, the process of forming separated particles by the coating substance and the anode material is inhibited, the heterogeneous nucleation and growth of the coating substance on the surface of the anode material are promoted, and the uniform coating or filling of the coating substance on the surface of the anode material particles is realized under the stirring action. The surface coating of the anode material, primary particle crystal boundary filling, surface element doping and other multiple surface modifications are realized through subsequent heat treatment, and the stability of the anode material is improved.
Preferably, when the ion exchange membrane is a cation exchange membrane, the positive electrode material is dispersed in the anion chamber; when the ion exchange membrane is an anion exchange membrane, dispersing the positive electrode material in a cation chamber; the particle size of the positive electrode material is 1-100 mu m.
Preferably, the cation solution or the anion solution is mixed with the anode material to obtain a mixed solution; the solid content of the anode material in the mixed solution is 2-20 wt%.
Preferably, the temperature of the precipitation reaction or the oxidation-reduction reaction is 20 to 100 ℃ and the time is 0.5 to 36 hours.
Preferably, the coating substance in the positive electrode material with the coating substance distributed on the surface comprises Mn (OH) 2 、Co(OH) 2 、 AlPO 4 、Mn 3 (PO 4 ) 2 、FePO 4 、Li 3 PO 4 、AlF 3 、LiAlO 2 、Li 2 ZrO 3 、Li 4 Ti 5 O1 2 、Al 2 O 3 、TiO 2 、 ZrO 2 、ZnO、Al(OH) 3 And Zr (OH) 4 One or more of (a); the mass of the coating substance is 0.1-10% of the mass of the positive electrode material (before modification). Wherein the drying is natural drying, drying and vacuum drying, the drying temperature is 20-150 ℃, and the drying time is 24-48 h.
Preferably, when the anode material is a lithiated anode material, the heat treatment temperature is 600-800 ℃, the heat treatment time is 2-10 hours, and the heat treatment atmosphere is pure oxygen or air. Or, when the anode material is an anode precursor material, mixing the obtained anode material with the coating substance distributed on the surface and lithium oxide for sintering treatment to obtain a surface modified anode material; the lithium-containing oxide includes LiOH H 2 O、LiNO 3 、Li 2 CO 3 、Li 2 O and Li 2 O 2 The molar ratio of the positive electrode material with the coating material distributed on the surface to the lithium-containing oxide is 1: (1.01-1.10).
Preferably, the sintering treatment comprises: one-step sintering or two-step sintering; the atmosphere of the sintering treatment is pure oxygen or air
Wherein the one-step sintering comprises: the sintering temperature is 600-850 ℃, the heat preservation time is 10-20 h, and the temperature rise rate of one-step sintering is preferably 2-5 ℃/min;
the two-step sintering comprises: the first step is that the sintering temperature is 300-500 ℃, and the heat preservation time is 2-4 h; the second step, sintering temperature is 700-850 ℃, and heat preservation time is 10-20 h; preferably, the heating rate of the two-step sintering is 2-5 ℃/min.
In a third aspect, the present invention provides a surface-modified positive electrode material prepared according to the above surface modification method.
In a fourth aspect, the present invention provides a lithium ion battery comprising: a negative electrode material, the surface-modified positive electrode material, and a separator or a solid electrolyte separating the surface-modified positive electrode material from the negative electrode material; preferably, the separator comprises a polypropylene separator (PP), a celgard separator, and the solid electrolyte comprises a garnet-type solid electrolyte, a NASICON-type solid electrolyte, a sulfide-type solid electrolyte, a perovskite-type solid electrolyte; preferably, the negative electrode material is graphite, silicon carbon, silicon dioxide, a silicon alloy, tin oxide, metallic lithium or a lithium alloy.
Has the beneficial effects that:
the invention uses an ion exchange membrane to selectively diffuse anions or cations, so that the anions and the cations are slowly combined to generate a precipitation reaction or generate an oxidation reduction reaction to generate a precipitate, thereby obtaining the coating substance. The device and the method enable the supersaturation degree of the coating substance in the mixed liquid system of the anode material to be always kept at a lower level, inhibit the process that the coating substance forms particles separated from the precursor material due to homogeneous nucleation and growth, promote the heterogeneous nucleation and growth of the coating substance on the surface of the precursor material, and further realize the uniform coating of the surface of the anode material under the action of solid-liquid phase shearing force provided by stirring;
according to the invention, the in-situ reaction is carried out on the surface of the precursor to realize uniform coating, and multiple surface modifications such as surface coating of the anode material, primary particle crystal boundary filling, surface element doping and the like can be realized through a heat treatment step, so that the stability of the active material is further improved under various synergistic effects;
the basic driving force of the coating is from ion diffusion, extra energy is not needed, the principle is simple, and the needed medicines and solvents are cheap and easy to obtain and are environment-friendly. Therefore, the method has the advantages of strong universality, convenient operation, environmental protection and higher industrial application value
Drawings
FIG. 1 is a device for modifying the surface of a cathode material of the present invention, wherein: 1-cation chamber, 2-anion chamber, 3-ion exchange membrane, 4-stirrer;
fig. 2 is an X-ray diffraction (XRD) pattern of a positive electrode material including example 1 having a surface modification and comparative example 1 having no surface modification;
FIG. 3 is a dQ/dV curve for different cycles of a positive electrode material, including example 1(B) with surface modification and comparative example 1(A) without surface modification;
FIGS. 4A and 4B are graphs comparing the cycling stability of surface modified examples 1-3 and comparative example 1 without surface modification;
FIG. 5 is a graph comparing the rate performance of example 1 with surface modification and comparative example 1 without surface modification;
fig. 6 is a Scanning Electron Micrograph (SEM) of a cross section of positive electrode particles before and after the circulation of the positive electrode material including example 1 subjected to surface modification and comparative example 1 not subjected to surface modification (both scales are 5 μm).
Detailed Description
The present invention is further illustrated by the following examples, which are to be construed as merely illustrative, and not a limitation of the present invention.
In the disclosure, the device for modifying the surface of the positive electrode material based on the ion exchange membrane comprises: comprises a cation chamber and an anion chamber, and a cation exchange membrane separating the anion chamber and the cation chamber; wherein the cation chamber and the anion chamber are both internally provided with stirring devices. When the device is used, the anode material mixed solution and the cation substance solution are prepared firstly, then the anode material mixed solution and the cation substance solution are respectively injected into the anion chamber and the cation chamber, and the stirring is always kept to be started when the device is coated.
In the invention, the preparation method comprises the steps of providing an anion substance solution and providing a cation substance solution, respectively placing anions and cations forming a coating substance in an anion chamber and a cation chamber, and optionally placing a positive electrode material in the anion chamber or the cation chamber to obtain a positive electrode material mixed solution. The anion and the cation of the coating substance are isolated by adopting an ion exchange membrane, the diffusion of the anion or the cation is controlled, the anion and the cation are slowly combined, a precipitation reaction or an oxidation reduction reaction is carried out to generate a precipitate, and the coating substance is obtained on the surface of the anode material or at the pore space of the particle. And separating, drying and thermally treating the obtained modified positive electrode material to obtain the surface modified positive electrode material. The method for modifying the surface of the cathode material using the device will be described in detail below
And (4) preparing an anion solution. Soluble materials which can provide anions of the coating materials are dissolved in a solvent to obtain an anion solution. Optionally, the positive electrode material is dispersed into the anion solution to obtain a positive electrode material mixed solution. More preferably, the positive electrode material mixed solution is injected into the anion chamber, and the cation solution is injected into the cation chamber. And then coating the positive electrode material, and centrifuging and drying the mixed solution in the anion chamber after the coating is finished to obtain the coated positive electrode material. During the coating process, the anion chamber and the cation chamber are always stirred. The centrifugation speed can be 3000-8000 rpm, and the centrifugation time can be 3-5 min. The drying is carried out at the temperature of 20-150 ℃ for 24-48 h or in vacuum.
And (4) preparing a cation solution. Soluble material that provides cations of the coating material is dissolved in a solvent, an anionic solution. Optionally, the positive electrode material is dispersed into the cation solution to obtain a positive electrode material mixed solution. More preferably, the positive electrode material mixed solution is injected into the cation chamber, and the anion solution is injected into the anion chamber. And then the pair is carried out. And coating the positive electrode material, and centrifuging and drying the mixed solution in the anion chamber after the coating is finished to obtain the coated positive electrode material. During the coating process, the anion chamber and the cation chamber are always stirred. The centrifugation speed can be 3000-8000 rpm, and the centrifugation time can be 3-5 min. The drying is carried out in vacuum or at the temperature of 20-150 ℃ for 24-48 h.
When the coated material is a lithiated positive electrode material, the obtained coated positive electrode material is subjected to heat treatment, the positive electrode material recovers electrochemical activity, and the coating substance coated on the surface of the positive electrode material can realize surface coating and/or element doping of the positive electrode material through heat treatment.
When the coated material is a positive electrode precursor material, the obtained coated positive electrode precursor material and LiOH & H 2 Mixing (for example, fully ball-milling and mixing) lithium-containing compounds such as O and the like according to a molar ratio of 1: x (1.01-1.10), sintering, wherein in the sintering process, a positive electrode precursor material and a lithium-containing oxide undergo a high-temperature solid-phase reaction to form a positive electrode material, and a coating substance coated on the surface of the positive electrode precursor material can realize surface coating of the positive electrode material and surface coating of the positive electrode material at high temperatureAnd/or element doping.
In the invention, the positive electrode material comprises a lithiated positive electrode material and a positive electrode precursor material. The particle size of the positive electrode material is 1-100 mu m. In an optional embodiment, the dispersion method of dispersing the positive electrode material into the cation solution or the anion solution to obtain the positive electrode material mixed solution is ultrasonic dispersion, the ultrasonic power is 100-500W, and the ultrasonic time is 1-180 min.
In the present invention, a lithium ion battery includes: positive electrode, negative electrode, and separator or solid electrolyte separating the positive and negative electrode materials. The positive electrode material of the battery is the surface modified positive electrode material based on the ion exchange membrane surface modification. The diaphragm or the solid electrolyte comprises PP, celgard, garnet type solid electrolyte, NASICON type solid electrolyte, sulfide type solid electrolyte and perovskite type solid electrolyte. The negative electrode is graphite, silicon carbon, silicon dioxide, silicon alloy, tin oxide, metal lithium or lithium alloy.
Specifically, the surface-modified positive electrode material, conductive carbon and a binder are uniformly mixed to prepare slurry, the slurry is coated on an aluminum foil, and the dried aluminum foil loaded with the slurry is cut into small round pieces by a cutting machine to be used as the positive electrode. And (5) forming a full cell and performing test characterization.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The device diagram as shown in fig. 1 is assembled. The ion exchange membrane used in the device is a proton exchange membrane Nafion 117 produced by DuPont, and the Nafion 117 membrane is firstly used at 80 ℃ and 5 wt% of H before use 2 O 2 Decocting in water for 1 hr to remove organic substances in the membraneImpurities. Secondly, repeatedly washing the membrane with deionized water, soaking the membrane in the deionized water at the temperature of 80 ℃ and boiling the membrane for 1 hour to completely remove residual H 2 O 2 . The membrane was again soaked at 80 ℃ in 5 wt% H 2 SO 4 Cooking the solution for 1 h. Finally, repeatedly washing the membrane by using deionized water, soaking the membrane in the deionized water with the temperature of 80 ℃ for heat treatment for 1 hour to completely remove residual H in the membrane 2 SO 4 . The purpose of the Nafion 117 treatment is to activate the proton exchange membrane to provide cation exchange.
Step 1): weighing NaOH and dissolving the NaOH in an aqueous solution to prepare a NaOH aqueous solution with the concentration of 0.1mol/L as an anion solution. 4g of nickel-cobalt-manganese ternary precursor material (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) And mixing the solution with the obtained anion solution according to the mass ratio of 1:20, and dispersing the mixed solution by using ultrasound for 10min to obtain a mixed solution of the anode material.
Step 2): taking MnCl 2 Dissolving in water to prepare 0.1mol/L MnCl 2 The solution (80mL) was used as the cationic solution.
And step 3): respectively injecting the anode material mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber, keeping the stirring of the anion chamber and the cation chamber to be always started, and coating the surface of the precursor for 4h at the coating temperature of 25 ℃. And after the coating is finished, centrifuging the mixed solution in the anion chamber at the rotating speed of 3000rpm for 3 min. And (3) drying the solid material obtained by centrifugation in a vacuum oven at the drying temperature of 80 ℃ for 24 hours. Obtaining surface Mn (OH) 2 And (3) a coated ternary positive electrode precursor material.
Step 4): mixing the coated ternary precursor material obtained in the step 3) with LiOH & H 2 Fully mixing O by ball milling according to the molar ratio of 1:1.05, and then sintering in two steps under the pure oxygen atmosphere: the sintering temperature of the first step is 400 ℃, and the heat preservation time is 2 hours; the second step is that the sintering temperature is 750 ℃, and the heat preservation time is 12 hours; the heating rate was 3 ℃/min. And obtaining the surface modified cathode material.
The obtained surface modified cathode materialThe material is used as a positive active material to prepare an electrode and assemble the button cell. Assembly and testing of CR2025 button cells: preparing a surface modified positive electrode material, conductive carbon (Super P: VGCF ═ 1:1) and polyvinylidene fluoride (PVDF) into slurry according to a mass ratio of 8:1:1, coating the slurry on an aluminum foil, cutting the dried aluminum foil loaded with the slurry into a small wafer with the diameter of 1.2cm by a cutting machine to be used as a positive electrode, taking a metal lithium wafer as a negative electrode, taking Celgard as a diaphragm and taking a 1M carbonate solution as an electrolyte (wherein the solvent is a mixed solution of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1, and the solute is LiPF 6 ) And assembling the button cell into a CR2025 button cell in an argon glove box.
Example 2
Step 1): NaOH is weighed and dissolved in the water solution to prepare 0.1mol/L anion solution. 4g of nickel-cobalt-manganese ternary precursor material (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the solution with the obtained anion solution according to the mass ratio of 1:20, and dispersing the mixed solution by using ultrasound for 10min to obtain a positive electrode material mixed solution;
step 2): taking Mn (C) 2 O 2 H 3 ) 2 Dissolving in water to obtain Mn (C) with concentration of 0.2mol/L 2 O 2 H 3 ) 2 Solution (80mL) as cationic solution;
and step 3): respectively injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber, keeping the anion chamber and the cation chamber to be stirred and opened all the time, and coating the surface of the precursor for 4 hours at the coating temperature of 25 ℃. And after the coating is finished, centrifuging the mixed solution in the anion chamber at the rotating speed of 3000rpm for 3 min. And (3) drying the solid material obtained by centrifugation in a vacuum oven at the drying temperature of 80 ℃ for 24 h. Obtaining surface Mn (OH) 2 A coated ternary positive precursor material;
and step 4): mixing the coated ternary precursor material obtained in the step 3) with LiOH & H 2 Fully mixing O by ball milling according to the molar ratio of 1:1.05, and then sintering in two steps under the pure oxygen atmosphere: first step of roastingThe junction temperature is 400 ℃, and the heat preservation time is 2 hours; the second step is that the sintering temperature is 750 ℃, and the heat preservation time is 12 hours; the heating rate was 3 ℃/min. Obtaining a surface modified anode material; the obtained surface modified cathode material was prepared into an electrode and assembled into a button cell, and the preparation process was the same as in example 1.
Example 3
Step 1): NaOH is weighed and dissolved in the water solution to prepare 0.1mol/L anion solution. 4g of nickel-cobalt-manganese ternary precursor material (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the solution with the obtained anion solution according to the mass ratio of 1:20, and dispersing the mixed solution by using ultrasound for 10min to obtain a positive electrode material mixed solution;
step 2): taking Co (C) 2 O 2 H 3 ) 2 Dissolving in water to obtain Co (C) with concentration of 0.2mol/L 2 O 2 H 3 ) 2 Solution (80mL) as cationic solution;
step 3): respectively injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber, keeping the stirring of the anion chamber and the cation chamber to be always started, and carrying out surface coating on the precursor for 4h at the coating temperature of 25 ℃. And after the coating is finished, centrifuging the mixed solution in the anion chamber at the rotating speed of 3000rpm for 3 min. And (3) drying the solid material obtained by centrifugation in a vacuum oven at the drying temperature of 80 ℃ for 24 h. Obtaining surface Co (OH) 2 A coated ternary positive precursor material;
step 4): mixing the coated ternary precursor material obtained in the step 3) with LiOH & H 2 Fully mixing O by ball milling according to the molar ratio of 1:1.05, and then sintering in two steps under the pure oxygen atmosphere: the sintering temperature of the first step is 400 ℃, and the heat preservation time is 2 hours; the second step, the sintering temperature is 750 ℃, and the heat preservation time is 12 hours; the temperature rise rate was 3 ℃/min. Obtaining a surface modified anode material; the obtained surface modified cathode material was prepared into an electrode and assembled into a button cell, and the preparation process was the same as in example 1.
Example 4
Step 1): weighing NaOH and dissolving inIn the aqueous solution, 0.1mol/L of an anionic solution was prepared. 4g of nickel-cobalt-manganese ternary precursor material (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) And mixing the solution with the obtained anion salt solution according to the mass ratio of 1:20, and dispersing the mixed solution by using ultrasound for 10min to obtain a mixed solution of the anode material.
Step 2): taking MnCl 2 And Co (NO) 3 ) 2 The cation solution (80mL) was prepared by dissolving the cation in water in a molar amount of 1:1 to give a 0.1mol/L solution.
And step 3): respectively injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber, keeping the stirring of the anion chamber and the cation chamber to be always started, and carrying out surface coating on the precursor for 4h at the coating temperature of 25 ℃. And after the coating is finished, centrifuging the mixed solution in the anion chamber at the rotating speed of 3000rpm for 3 min. And (3) drying the solid material obtained by centrifugation in a vacuum oven at the drying temperature of 80 ℃ for 24 h. Obtaining surface Mn f Co g (OH) 2 (f + g ═ 1) a coated ternary positive electrode precursor material.
Step 4): mixing the coated ternary precursor material obtained in the step 3) with LiOH & H 2 Fully mixing O by ball milling according to the molar ratio of 1:1.05, and then sintering in two steps under the pure oxygen atmosphere: the sintering temperature of the first step is 400 ℃, and the heat preservation time is 2 hours; the second step is that the sintering temperature is 750 ℃, and the heat preservation time is 12 hours; the heating rate was 3 ℃/min. And obtaining the surface modified cathode material.
The obtained surface modified cathode material was prepared into an electrode and assembled into a button cell in the same process as in example 1.
Example 5
Step 1): weighing (NH) 4 ) 2 HPO 4 Dissolving in water solution to prepare 0.1mol/L anion solution. 4g of nickel-cobalt-manganese ternary precursor material (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the solution with the obtained anion solution according to the mass ratio of 1:20, and dispersing the mixed solution by using ultrasound for 10min to obtain a positive electrode material mixed solution;
step 2): taking Al (NO) 3 ) 3 ·9H 2 Dissolving O in water to prepare a cationic solution (80mL) of 0.1 mol/L;
step 3): respectively injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber, keeping the anion chamber and the cation chamber to be stirred and opened all the time, and coating the precursor for 4h at the coating temperature of 25 ℃. And after the coating is finished, centrifuging the mixed solution in the anion chamber at the rotating speed of 3000rpm for 3 min. And (3) drying the solid material obtained by centrifugation in a vacuum oven at the drying temperature of 80 ℃ for 24 hours. Obtaining AlPO 4 A coated ternary positive precursor material;
step 4): mixing the coated ternary precursor material obtained in the step 3) with LiOH & H 2 Fully mixing O by ball milling according to the molar ratio of 1:1.05, and then sintering in two steps under the pure oxygen atmosphere: the sintering temperature of the first step is 400 ℃, and the heat preservation time is 2 hours; the second step, the sintering temperature is 750 ℃, and the heat preservation time is 12 hours; the heating rate was 3 ℃/min. And obtaining the surface modified cathode material.
The surface modified positive electrode material was prepared into an electrode and a coin cell was assembled in the same procedure as in example 1.
Example 6
Step 1): weighing LiOH. H 2 Dissolving O in the water solution to prepare 0.1mol/L anion solution. 4g of nickel-cobalt-manganese ternary precursor material (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the solution with the obtained anion solution according to the mass ratio of 1:20, and dispersing the mixed solution by using ultrasound for 10min to obtain a positive electrode material mixed solution;
step 2): taking Al (NO) 3 ) 3 ·9H 2 Dissolving O in water to prepare a cationic solution (80mL) of 0.1 mol/L;
step 3): respectively injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber, keeping the stirring of the anion chamber and the cation chamber to be always started, and coating the precursor for 4h at the coating temperature of 25 ℃. Coating timeAnd after the end, centrifuging the mixed solution in the anion chamber at the rotating speed of 3000rpm for 3 min. And (3) drying the solid material obtained by centrifugation in a vacuum oven at the drying temperature of 80 ℃ for 24 h. Obtaining LiAlO 2 A coated ternary positive precursor material;
step 4): mixing the coated ternary precursor material obtained in the step 3) with LiOH & H 2 Fully ball-milling and mixing O according to the molar ratio of 1:1.05, and then sintering in two steps under the pure oxygen atmosphere, wherein the sintering temperature in the first step is 400 ℃, and the heat preservation time is 2 hours; the second step, the sintering temperature is 750 ℃, and the heat preservation time is 12 hours; the heating rate was 3 ℃/min. And obtaining the surface modified cathode material.
The obtained surface-modified cathode material was prepared into an electrode and assembled into a coin cell, in the same procedure as in example 1.
Example 7
Step 1): weighing LiOH. H 2 Dissolving O in the water solution to prepare 0.1mol/L anion solution. 4g of nickel-cobalt-manganese ternary precursor material (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Mixing the solution with the obtained anion solution according to the mass ratio of 1:20, and dispersing the mixed solution by using ultrasound for 10min to obtain a positive electrode material mixed solution;
step 2): taking 0.49g of ZrO (NO) 3 ) 2 ·5H 2 Dissolving O in water to prepare a cationic solution (80mL) of 0.1 mol/L;
step 3): respectively injecting the precursor mixed solution obtained in the step 1) and the cation solution obtained in the step 2) into an anion chamber and a cation chamber, keeping the stirring of the anion chamber and the cation chamber to be always started, and carrying out ZrO on the precursor 2 And (4) coating, wherein the coating time is 4h, and the coating temperature is 25 ℃. And after the coating time is over, centrifuging the mixed solution in the anion chamber at the rotating speed of 3000rpm for 3 min. And (3) drying the solid material obtained by centrifugation in a vacuum oven at the drying temperature of 80 ℃ for 24 h. Obtaining ZrO 2 A coated ternary positive electrode precursor material;
step 4): mixing the coated ternary precursor material obtained in the step 3) with LiOH & H 2 According to the molar ratio of O1:1.05, fully mixing by ball milling, and then sintering in two steps under pure oxygen atmosphere: the sintering temperature of the first step is 400 ℃, and the heat preservation time is 2 hours; the second step is that the sintering temperature is 750 ℃, and the heat preservation time is 12 hours; the heating rate was 3 ℃/min. And obtaining the surface modified cathode material.
The obtained surface-modified cathode material was prepared into an electrode and assembled into a button cell, in the same manner as in example 1.
Comparative example 1
Preparing nickel-cobalt-manganese ternary precursor material (Ni) 0.83 Co 0.12 Mn 0.05 (OH) 2 ) Directly react with LiOH. H 2 Fully mixing O by ball milling according to the molar ratio of 1:1.05, and then sintering in two steps under the pure oxygen atmosphere: the sintering temperature of the first step is 400 ℃, and the heat preservation time is 2 hours; the second step is that the sintering temperature is 750 ℃, and the heat preservation time is 12 hours; the heating rate was 3 ℃/min. And obtaining the surface modified cathode material.
The obtained surface-modified cathode material was prepared into an electrode and assembled into a coin cell, the procedure of which was the same as in example 1.
Fig. 1 shows a device for modifying the surface of a positive electrode. The device is mainly divided into a cation chamber, an anion chamber, an ion exchange membrane and a stirring or flow system. When the ion exchange membrane is used, anions and cations forming the coating substance are respectively placed in the anion chamber and the cation chamber, and the positive electrode material can be optionally placed in the anion chamber or the cation chamber according to the type of the selected ion exchange membrane to obtain a positive electrode material mixed solution. The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the embodiments and devices. It is to be understood that the application is not limited to the details or methodology set forth in the description or illustrated in the drawings. It is also to be understood that the terminology used in the disclosure is for the purpose of description only and should not be regarded as limiting.
Fig. 2 shows an X-ray diffraction (XRD) pattern of the positive electrode, the positive electrode material including example 1 having surface modification and comparative example 1 having no surface modification. All diffraction peaks are similar to the typical hexagonal a-NaFeO 2 The structure (JCPDF card number 01-089-4533, space group R-3m) which represents the principal phase of NCM is well matched. a-NaFeO 2 Crystal structure of typeFor the ordered rock-salt form, the Li and Me ions occupy alternating (111) layers. NCM having layered NaFeO 2 Structure, R-3m space group, made of LiO 6 And MO 6 The octahedra form alternating layers. As can be seen from fig. 1, the main diffraction peaks of all samples match well with the JCPDF card with R-3m space group. It is shown that the surface modification according to the method of the invention does not change the layer structure of the NCM material.
Fig. 3 shows the dQ/dV curves for different numbers of cycles for a positive electrode material comprising example 1(B) surface modified and comparative example 1(a) not surface modified. The dQ/dV curve shows that after circulation, the peak position of the dQ/dV curve of the comparative example 1 is seriously displaced, and the charging peak moves rightwards, which indicates that the material is seriously polarized in the circulation process; the phase transition peaks H2-H3 at high voltage gradually disappear, which indicates that the high-voltage anode material has serious phase transition. In contrast, the position of the peak of example 1 is not significantly shifted, indicating that the positive electrode material undergoes less polarization and phase change during cycling. The surface modification method of the nickel-cobalt-manganese ternary cathode material based on the ammonolysis reaction is fully shown to be beneficial to inhibiting polarization and phase change of the cathode material in the circulating process.
Fig. 4A and 4B compare the cycle performance of the positive electrode materials obtained in example 1, example 2 and example 3, which were surface-modified, and comparative example 1, which was not surface-modified. The result shows that the cycle performance of the cathode material subjected to surface modification by the method is obviously improved, and after the cathode material is cycled under the same conditions, the capacity retention rate of the cathode material subjected to surface modification is obviously higher than that of the cathode material not subjected to surface modification, which indicates that the cycle stability of the cathode material can be obviously improved by the surface modification implemented by the method. The effectiveness of the device and the method for modifying the surface of the positive electrode material based on the ion exchange membrane is fully demonstrated.
Fig. 5 shows a graph of the magnification comparison of the positive electrode material including example 1 with surface modification and comparative example 1 without surface modification. The result shows that the multiplying power performance of the nickel-cobalt-manganese cathode material subjected to surface modification by the device and the method for surface modification of the cathode material based on the ion exchange membrane is remarkably improved, more capacity can be released under a high multiplying power state, and the device and the method for surface modification of the cathode material based on the ion exchange membrane are fully shown to be capable of improving the multiplying power performance of the cathode material.
Fig. 6 shows SEM images of cross sections of the cathode particles before and after cycling of the cathode material, which includes surface-modified example 1 and unmodified comparative example 1. The results show that example 1 and comparative example 1 are secondary particles formed by agglomeration of primary particles, the primary particles are tightly bonded before circulation, and no cracks are evident between the secondary particles. After 150 cycles at 1C rate, the morphology of the spherical secondary particles is maintained completely in example 1, while the positive electrode particles in comparative example 1 are broken significantly. The device and the method for modifying the surface of the positive electrode material based on the ion exchange membrane are shown to be capable of inhibiting the particle breakage of the positive electrode material in the circulation process.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (16)
1. A device for surface modification of a positive electrode material based on an ion exchange membrane is characterized by comprising:
a cation chamber containing a cation solution therein;
an anion chamber containing an anion solution therein;
an ion exchange membrane for physical separation of an anion chamber and a cation chamber, the ion exchange membrane comprising a cation exchange membrane and an anion exchange membrane;
and the stirring system is respectively arranged at the bottom of the cation chamber and the bottom of the anion chamber or/and the flowing system is respectively communicated and connected with the cation chamber and the anion chamber.
2. The apparatus for surface modification of an ion exchange membrane based cathode material according to claim 1, wherein the flow system comprises:
a cation solution storage tank, a flow pump and a flow pipeline which are communicated with the cation chamber and the cation solution storage tank;
an anion solution storage tank, a flow pump and a flow pipeline which are communicated with the anion chamber and the anion solution storage tank.
3. The apparatus for surface modification of an ion exchange membrane based positive electrode material according to claim 1, wherein the stirring system comprises at least one of a magnetic stirring apparatus, a mechanical stirring apparatus and an ultrasonic stirring apparatus, which are respectively disposed at the bottom of the anion chamber and the bottom of the anion chamber.
4. The device for surface modification of the ion exchange membrane-based cathode material according to claim 1, wherein the active group in the cation exchange membrane comprises at least one of a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, a phenol group, an arsenic acid group and a selenoic acid group; the active groups in the anion exchange membrane comprise at least one of amino and arylamino of primary, secondary, tertiary and quaternary amines.
5. The device for surface modification of the ion exchange membrane based positive electrode material according to claim 1, wherein the positive electrode material comprises a lithiated positive electrode material and a positive electrode precursor material;
the lithiated positive electrode material comprises LiNi b Co c Mn 1-b-c O 2 (wherein b is more than or equal to 0 and less than or equal to 1, and c is more than or equal to 0 and less than or equal to 1); and LiNi m Co n Al 1-m-n O 2 (0≤m≤1，0≤n≤1)；
The positive electrode precursor material includes Ni (1-y-z) Co y Mn z (OH) 2 (wherein y is 0. ltoreq. y.ltoreq.1, z is 0. ltoreq. z.ltoreq.1) and Ni (1-a-d) Co a Al d (OH) 2 (wherein a is more than or equal to 0 and less than or equal to 1, and d is more than or equal to 0 and less than or equal to 1).
6. The surface modification of the ion exchange membrane-based positive electrode material according to any one of claims 1 to 5Wherein the solute in the cationic solution is selected from the group consisting of Al (NO) 3 ) 3 、Al 2 (SO 4 ) 3 、AlCl 3 、MnCl 3 、Co(NO 3 ) 3 、Co 2 (SO 4 ) 3 、Fe(NO 3 ) 3 、Fe 2 (SO 4 ) 3 、FeCl 3 、Cr(NO 3 ) 3 、Cr 2 (SO 4 ) 3 、CrCl 3 、Zr(NO 3 ) 4 、ZrCl 4 、Zn(NO 3 ) 3 、TiBr 4 At least one of (a);
the solvent in the cationic solution comprises at least one of distilled water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cycloethanol, acetone, cyclohexanone, glycerol and ethyl acetate;
the concentration of the cation solution is 0.01-10 mol/L.
7. The apparatus for surface modification of an ion-exchange membrane based cathode material according to any one of claims 1 to 6, wherein the solute in the anion solution is selected from KOH, NaOH, LiOH, (NH) 4 ) 2 HPO 4 、NH 4 H 2 PO 4 、H 3 PO 4 、NH 3 ·H 2 At least one of KF in O, LiF and NaF;
the solvent in the anion solution comprises at least one of distilled water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cycloethanol, acetone, cyclohexanone, glycerol and ethyl acetate;
the concentration of the anion solution is 0.01 mol/L-10 mol/L;
preferably, the device for modifying the surface of the positive electrode material based on the ion exchange membrane further comprises an external power supply connected with the cation chamber and the anion chamber.
8. A method for modifying the surface of a positive electrode material, comprising:
(1) dispersing a positive electrode material in a cation solution or an anion solution in the device for modifying the surface of the positive electrode material based on the ion exchange membrane, which is disclosed by claim 1, combining the anion solution with the cation solution through a stirring system or a flowing system, and carrying out a precipitation reaction or an oxidation reduction reaction to generate a precipitate, so that a coating substance is formed on the surface of the positive electrode material or at the particle pores of the positive electrode material, and then separating and drying the coating substance to obtain the positive electrode material with the coating substance distributed on the surface;
(4) and carrying out heat treatment on the positive electrode material with the coating substance distributed on the surface to obtain the surface modified positive electrode material.
9. The surface modification method according to claim 8, wherein when the ion exchange membrane is a cation exchange membrane, the positive electrode material is dispersed in the anion chamber; when the ion exchange membrane is an anion exchange membrane, dispersing the positive electrode material in the cation chamber; the particle size of the positive electrode material is 1-100 mu m.
10. The surface modification method according to claim 8, wherein a mixed solution is obtained by mixing a cation solution or an anion solution with a positive electrode material; the solid content of the anode material in the mixed solution is 2-20 wt%;
the temperature of the precipitation reaction or the oxidation-reduction reaction is 20-100 ℃, and the time is 0.5-36 hours.
11. The method of claim 8, wherein the coating substance in the positive electrode material with the coating substance distributed on the surface comprises Mn (OH) 2 、Co(OH) 2 、AlPO 4 、Mn 3 (PO 4 ) 2 、FePO 4 、Li 3 PO 4 、AlF 3 、LiAlO 2 、Li 2 ZrO 3 、Li 4 Ti 5 O1 2 、Al 2 O 3 、TiO 2 、ZrO 2 、ZnO、Al(OH) 3 And Zr (OH) 4 One or more of; the mass of the coating substance is 0.1-10% of the mass of the positive electrode material.
12. The surface modification method according to any one of claims 8 to 11, wherein when the positive electrode material is a lithiated positive electrode material, the heat treatment temperature is 600 to 800 ℃, the heat treatment time is 2 to 10 hours, and the heat treatment atmosphere is pure oxygen or air.
13. The surface modification method according to any one of claims 8 to 11, wherein when the positive electrode material is a positive electrode precursor material, the obtained positive electrode material with the coating substance distributed on the surface is mixed with lithium oxide to be subjected to sintering treatment to obtain a surface modified positive electrode material; the lithium-containing oxide includes LiOH H 2 O、LiNO 3 、Li 2 CO 3 、Li 2 O and Li 2 O 2 The molar ratio of the positive electrode material with the coating substance distributed on the surface to the lithium-containing oxide is 1: (1.01-1.10).
14. The surface modification method of claim 13, wherein the sintering process comprises: one-step sintering or two-step sintering; the atmosphere of the sintering treatment is pure oxygen or air
Wherein the one-step sintering comprises: the sintering temperature is 600-850 ℃, the heat preservation time is 10-20 h, and the temperature rise rate of one-step sintering is preferably 2-5 ℃/min;
the two-step sintering comprises: the first step sintering temperature is 300-500 ℃, and the heat preservation time is 2-4 h; the second step, sintering temperature is 700-850 ℃, and heat preservation time is 10-20 h; preferably, the heating rate of the two-step sintering is 2-5 ℃/min.
15. A surface-modified positive electrode material prepared according to the surface modification method of any one of claims 8 to 14.
16. A lithium ion battery comprising: a negative electrode material, the surface-modified positive electrode material as claimed in claim 15, and a separator or a solid electrolyte separating the surface-modified positive electrode material and the negative electrode material;
preferably, the separator comprises a polypropylene separator (PP), a celgard separator, and the solid electrolyte comprises a garnet-type solid electrolyte, a NASICON-type solid electrolyte, a sulfide-type solid electrolyte, a perovskite-type solid electrolyte;
preferably, the negative electrode material is graphite, silicon carbon, silicon dioxide, a silicon alloy, tin oxide, metallic lithium or a lithium alloy.
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