CN115084516B - Preparation method of boron-based multi-element composite material - Google Patents
Preparation method of boron-based multi-element composite material Download PDFInfo
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 59
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims description 34
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 32
- 239000004327 boric acid Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052755 nonmetal Inorganic materials 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000654 additive Substances 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 9
- 230000000996 additive effect Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 2
- 239000011343 solid material Substances 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011247 coating layer Substances 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
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of lithium ion batteries and sodium ion batteries, and discloses a preparation method of a boron-based multi-element composite material. The boron-based multi-element composite material is adopted to modify the battery material, and has the advantages of small additive consumption and uniform element distribution. Meanwhile, the problems of increased process cost, layering and enrichment of additive elements and the like caused by the need of multiple times of sintering when the battery material is used for various additives are solved, and the advantages of improving the specific capacity, coulombic efficiency, high-low temperature performance, cycle performance and the like of the battery anode material, improving the conductivity of the battery solid material, the structural strength of the material in the cycle and the like can be realized by selecting different additive element schemes.
Description
Technical Field
The invention relates to the technical field of ion batteries, in particular to a preparation method of a boron-based multi-element composite material.
Background
At present, the lithium ion battery occupies the important position of the development of new energy industry by the advantages of high specific energy, long service life, environmental protection and the like; energy density, safety, cycle life, cost and the like are key performance indexes of the lithium ion battery, and are also important directions of development of new energy industry. The positive electrode material is used as a core material of the lithium ion battery, and not only occupies 30% -40% of the manufacturing cost of the lithium ion battery, but also is a key factor for determining the improvement of the performance of the lithium ion battery. Taking the mainstream ternary positive electrode material as an example, in order to obtain higher specific energy density, industry struggles to develop ternary positive electrode materials with higher nickel content and higher use voltage. However, as the nickel content and the voltage used are increased, the thermal stability of the material becomes worse, and the safety of the battery is more challenging; the heat stability of the material can be improved and the electrochemical performance of the material can be improved by doping and coating modification of the positive electrode material, so that the energy density, the safety and the cycle life of the lithium ion battery are comprehensively improved, and the method is a core technology for modifying the positive electrode material.
However, the additive used for doping and coating is mainly a monobasic cationic compound, and various additives are mixed for use in synthesizing the positive electrode material or are subjected to a multi-sintering process. The problems of uneven distribution of different added elements, increased process cost and the like exist.
Disclosure of Invention
The invention aims to provide a preparation method of a boron-based multi-element composite material, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A preparation method of a boron-based multi-element composite material comprises the following steps:
1) Preparing nano slurry: weighing metal or nonmetal compound powder with a designed weight, placing the powder in a sand mill, adding a dispersing agent, and grinding until the fineness of the slurry is less than or equal to 500nm.
2) Preparing boron-based slurry: weighing boron-containing raw materials with designed weight, and dissolving the raw materials in a solvent to prepare boric acid solution. Adding boric acid solution into the sanded nano slurry, and fully mixing until the mixture is uniform.
3) Preparing a composite material: and drying, crushing or grading the uniformly mixed slurry to obtain the nano material of the boron-based multi-element composite additive.
As still further aspects of the invention: the particle size of the boric acid substrate is 0.5-20 mu m, and the nano metal or nonmetal compound is as follows: the particle size of Nano-X is 10nm-500nm.
As still further aspects of the invention: nano metal or non-metal compound: x in Nano-X includes, but is not limited to, one or more of the following element groups Ti, zr, al, mg, zn, V, ru, Y, W, na, K, rb, cs, sc, nb, bi, co, ni, mn, mo, ta, sr, la, nano-X refers to a combination of oxides, carbonates, sulfates, chlorides, acetates, phosphates, etc. of the above X elements.
As still further aspects of the invention: the proportion of boric acid and the nano metal or nonmetal loaded compound can be regulated and controlled according to the design, and the preferable element proportion is B: X= (0.05-1).
As still further aspects of the invention: the boron-containing raw material can be boric acid (H3 BO 3), metaboric acid (HBO 2), boron oxide (B2O 3) and the like.
As still further aspects of the invention: the dispersing agent in step 1) and the solvent in step 2) can be deionized water, ethanol, methanol, acetone, diethyl ether.
As still further aspects of the invention: the drying in the step 3) may be a drying method for removing the solvent such as spray drying, microwave drying, air drying, flash evaporation, freeze drying, etc.; the crushing or grading is process optimization control for improving the consistency of the product quality, and is not limited to the crushing and grading mode.
Compared with the prior art, the invention has the beneficial effects that: the boron-based multi-element composite material is adopted to modify the battery material, and has the advantages of small additive consumption and uniform element distribution. Meanwhile, the problems of increased process cost, layering and enrichment of additive elements and the like caused by the need of multiple times of sintering when the battery material uses multiple additives are solved.
By selecting different additive element schemes, the specific capacity, coulombic efficiency, high-low temperature performance, cycle performance and other performances of the battery anode material can be improved, the conductivity of the battery solid material, the structural strength of the material in the cycle and other beneficial effects can be improved, and the prepared boron-based multi-element composite material can be applied to lithium ion batteries and sodium ion batteries.
Drawings
FIG. 1 is a schematic structural diagram of a boron-based multi-element composite material provided by the invention;
FIG. 2 is a process flow diagram of a method of preparing a boron-based elemental composite;
Fig. 3 is an SEM photograph of the boron-based TiO2 composite prepared in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a boron-based multi-element composite material Nano-Ti@H3BO3 comprises the following steps:
1) Preparing nano slurry: weighing 100g of TiO 2 powder, placing in a sand mill, adding dispersant deionized water with the solid content of 20%, and sanding to the fineness of 20nm;
2) Preparing boron-based slurry: and (3) weighing boric acid H3BO3 according to the atomic ratio B of Ti=0.5, fully dissolving in 1000mL of deionized water to prepare boric acid solution, adding the boric acid solution into the sanded TiO2 nano slurry, and fully mixing until the mixture is uniform.
3) Preparing a composite material: and (3) carrying out spray drying on the uniformly mixed boron-based slurry, wherein the drying temperature is set to be 120 ℃. And obtaining the boron-based multi-element composite material Nano-Ti@H3BO3 after cyclone classification.
The boron-based multi-element composite material Nano-Ti@H3BO3 prepared by the method is used for coating and modifying the positive electrode material NCM811 of the lithium ion battery, and the test steps are as follows:
1) Weighing a certain weight of positive electrode material NCM811 of the lithium ion battery and Nano-Ti@H3BO3 with the mass ratio of 1%, and placing the materials in a high-speed mixer for uniform mixing.
2) And (3) placing the mixed materials in a high-temperature reaction furnace for roasting, wherein the roasting temperature is 400 ℃, and the sintering time is 12 hours.
Example 2
A preparation method of a boron-based multi-element composite material Nano-Al@H3BO3 comprises the following steps:
1) Preparing nano slurry: 100g of Al 2O3 powder is weighed and placed in a sand mill, absolute ethyl alcohol serving as a dispersing agent is added, the solid content is 10%, and sand milling is carried out until the fineness of the slurry is 50nm.
2) Preparing boron-based slurry: boric acid H3BO3 is weighed according to the atomic ratio B, al=0.7, and fully dissolved in 2000mL of absolute ethyl alcohol to prepare boric acid solution. Adding boric acid solution into the sanded Al2O3 nano slurry, and stirring and fully mixing until the mixture is uniform.
3) Preparing a composite material: and carrying out microwave drying on the uniformly mixed boron-based slurry, wherein the drying temperature is set to be 200 ℃. After crushing, the Nano-Al@H3BO3 of the boron-based multi-element composite material is obtained.
The boron-based multi-element composite material Nano-Al@H3BO3 prepared by the method is used for coating and modifying the positive electrode material NCM811 of the lithium ion battery, and the test steps are as follows:
1) Weighing a certain weight of positive electrode material NCM811 of the lithium ion battery and Nano-Al@H3BO3 with the mass ratio of 1%, and placing the materials in a high-speed mixer for uniform mixing.
2) And (3) placing the mixed materials in a high-temperature reaction furnace for roasting, wherein the roasting temperature is 400 ℃, and the sintering time is 12 hours.
Example 3
A preparation method of a boron-based multi-element composite material Nano-Zr@H3BO3 comprises the following steps:
1) Preparing nano slurry: 100g of ZrO 2 powder is weighed, placed in a sand mill, added with dispersant diethyl ether, and sanded until the fineness of the slurry is 500nm, wherein the solid content is 50%.
2) Preparing boron-based slurry: according to the atomic ratio B, al=1.0, weighing diboron trioxide B2O3, and fully dissolving in 1500mL of diethyl ether to prepare boric acid solution. Adding boric acid solution into the ZrO2 nano slurry after sanding, and stirring and fully mixing until the mixture is uniform.
3) Preparing a composite material: and carrying out microwave drying and forced air drying on the uniformly mixed boron-based slurry, wherein the drying temperature is set to be 60 ℃. After crushing, the Nano-Zr@H3BO3 of the boron-based multi-element composite material is obtained.
The boron-based multi-element composite material Nano-Zr@H3BO3 prepared by the method carries out coating modification on the positive electrode material NCM811 of the lithium ion battery, and the test steps are as follows:
1) Weighing a certain weight of positive electrode material NCM811 of the lithium ion battery and Nano-Zr@H3BO3 with the mass ratio of 2%, and placing the materials in a high-speed mixer for uniform mixing.
2) And (3) placing the mixed materials in a high-temperature reaction furnace for roasting, wherein the roasting temperature is 400 ℃, and the sintering time is 12 hours.
Example 4
A preparation method of a boron-based multi-element composite material Nano-V@H3BO3 comprises the following steps:
1) Preparing nano slurry: 100g of V2O5 powder is weighed, placed in a sand mill, added with a dispersing agent methanol, and sanded until the fineness of the slurry is 100nm, wherein the solid content is 50%.
2) Preparing boron-based slurry: and (3) weighing and fully dissolving the metaboric acid HBO2 into 100mL of methanol according to the atomic ratio B, V=0.05 to prepare a boric acid solution. Adding boric acid solution into the V2O5 nano slurry after sanding, and stirring and fully mixing until the mixture is uniform.
3) Preparing a composite material: and carrying out microwave drying and forced air drying on the uniformly mixed boron-based slurry, wherein the drying temperature is set to be 60 ℃. After crushing, the Nano-V@H3BO3 of the boron-based multi-element composite material is obtained.
The boron-based multi-element composite material Nano-V@H3BO3 prepared by the method is used for coating and modifying the positive electrode material NCM811 of the lithium ion battery, and the test steps are as follows:
1) Weighing a certain weight of positive electrode material NCM811 of the lithium ion battery and Nano-V@H3BO3 with the mass ratio of 0.5%, and placing the materials in a high-speed mixer for uniform mixing.
2) And (3) placing the mixed materials in a high-temperature reaction furnace for roasting, wherein the roasting temperature is 400 ℃, and the sintering time is 12 hours.
Example 5
A preparation method of a boron-based multi-element composite material Nano-Sr@H3BO3 comprises the following steps:
1) Preparing nano slurry: 100g of SrCO 3 powder is weighed, placed in a sand mill, added with dispersant deionized water, and sanded until the fineness of the slurry is 25nm.
2) Preparing boron-based slurry: boric acid H3BO3 is weighed according to the atomic ratio B, sr=0.1 and fully dissolved in 200mL of deionized water to prepare boric acid solution. Adding boric acid solution into the sanded SrCO3 nano slurry, and stirring and fully mixing until the mixture is uniform.
3) Preparing a composite material: and (3) placing the uniformly mixed boron-based slurry in a freeze dryer, and setting the freeze drying temperature to be-50 ℃. Crushing the dried powder to obtain the boron-based multi-element composite material Nano-Sr@H3BO3.
The boron-based multi-element composite material Nano-Sr@H3BO3 prepared by the method is used for coating and modifying the positive electrode material NCM811 of the lithium ion battery, and the test steps are as follows:
1) Weighing a certain weight of positive electrode material NCM811 of the lithium ion battery and Nano-Sr@H3BO3 with the mass ratio of 0.05%, and placing the materials in a high-speed mixer for uniform mixing.
2) And (3) placing the mixed materials in a high-temperature reaction furnace for roasting, wherein the roasting temperature is 400 ℃, and the sintering time is 12 hours.
Comparative example 1
Compared with example 1, the coating modification is carried out on the positive electrode material NCM811 of the lithium ion battery by adopting TiO2 and H3BO3 which are directly mixed, and the test steps are as follows:
1) Weighing a certain weight of a positive electrode material NCM811 of the lithium ion battery and a mixture of TiO2 and H3BO3 with the mass ratio of 1%, wherein the atomic ratio of B to Ti in the mixture of TiO 2 and H3BO3 is 0.5. Placing the materials in a high-speed mixer, and uniformly mixing.
2) And (3) placing the mixed materials in a high-temperature reaction furnace for roasting, wherein the roasting temperature is 400 ℃, and the sintering time is 12 hours.
Experimental conditions:
Table 1 lists the reversible specific capacities and first coulombic efficiencies of assembled lithium ion button cells 0.1C using the samples prepared in the examples and comparative examples above. The test conditions for the coin cells were LR 2032, 0.1C3.0-4.25V, vs. Li+/Li. The charge and discharge equipment used is a blue electricity charge and discharge instrument.
Table 1 comparison table of first charge and discharge properties
As can be seen from the data in the table, the Nano-ti@h3bo3 of the boron-based multi-element composite material prepared in example 1 of the present invention adopts the same coating element and the same coating dosage as those of comparative example 1, and uses the same treatment process, but the specific discharge capacity and coulombic efficiency of the sample of example 1 are obviously superior to those of comparative example. This is because Ti and B elements in the coating layer of the sample surface of the modified NCM811 of example 1 form a uniformly dispersed composite. In the synthesis process, nano TiO2 particles are synchronously diffused in the softening process of boric acid, so that the Ti and B in the composite material are distributed more uniformly on the surface of the high-nickel material, the crystal defect repair of the coating element on the surface of the high-nickel material is more perfect, and the material capacity can be fully exerted. In contrast, in the coating process of the NCM811 sample in comparative example 1, tiO2 and H3BO3 are in relatively free states, and the particle sizes of nano TiO2 and micro H3BO3 are greatly different, so that uniform distribution is not easy to form. The uniformity of improvement on the surface of the high-nickel material is low, the capacity of the material is not fully exerted, and the coulomb efficiency is reduced.
Table 2 lists the capacity retention rates for 50 weeks of reversible capacity of assembled lithium ion button cells using the samples prepared in the examples above. The test conditions for the cells were LR 2032, 45℃and 1C 3.0-4.25V, vs. Li+/Li. The charge and discharge equipment used is a blue electricity charge and discharge instrument.
Table 2 comparison of cycle performance
As can be seen from the data in the table, the boron-based multi-element composite material prepared by the invention has good capacity retention rate compared with the comparative example. Therefore, the boron-based multi-element composite material designed by the invention plays a good role in inhibiting the cyclic attenuation of the material for the high-nickel material.
The foregoing description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (3)
1. The preparation method of the boron-based multi-element composite material is characterized by comprising the following steps of:
1) Preparing nano slurry: weighing metal or nonmetal compound powder with a designed weight, placing the powder in a sand mill, adding a dispersing agent to prepare slurry, and grinding until the fineness of the slurry is less than or equal to 500nm;
2) Preparing boron-based slurry: weighing boron-containing raw materials with designed weight, dissolving the boron-containing raw materials in a solvent to prepare boric acid solution, adding the boric acid solution into the sanded nano slurry, and fully and uniformly mixing the boric acid solution and the sanded nano slurry;
3) Preparing a composite material: drying, crushing or grading the uniformly mixed slurry to obtain a boron-based multi-element composite material;
Wherein the metal or nonmetal compound is TiO 2、Al2O3、ZrO2、V2O5 or SrCO 3; the boron-containing raw material is boric acid, metaboric acid or boron oxide; the particle size of the boron-containing raw material is 0.5-20 mu m, and the particle size of the metal or nonmetal compound is 10-500 nm;
the molar ratio of boron element in the boric acid solution to Ti, al, zr, V or Sr element in the metal or nonmetal compound is 0.05-1.
2. The method of preparing a boron-based elemental composite according to claim 1 wherein the dispersant of step 1) and the solvent of step 2) are deionized water, ethanol, methanol, acetone or diethyl ether.
3. The method of claim 1, wherein the drying in step 3) is spray drying, microwave drying, air drying, flash evaporation or freeze drying.
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