CN111710917B - Manganese lithium ion battery for direct-current power supply and preparation method thereof - Google Patents
Manganese lithium ion battery for direct-current power supply and preparation method thereof Download PDFInfo
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- CN111710917B CN111710917B CN202010575015.6A CN202010575015A CN111710917B CN 111710917 B CN111710917 B CN 111710917B CN 202010575015 A CN202010575015 A CN 202010575015A CN 111710917 B CN111710917 B CN 111710917B
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 58
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 238000010030 laminating Methods 0.000 claims abstract description 3
- 239000013543 active substance Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 239000006258 conductive agent Substances 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 28
- 239000011149 active material Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000003292 glue Substances 0.000 claims description 20
- 239000002033 PVDF binder Substances 0.000 claims description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000006230 acetylene black Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011267 electrode slurry Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000007770 graphite material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000006256 anode slurry Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 229910052711 selenium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003475 lamination Methods 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009817 primary granulation Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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Images
Classifications
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a manganese lithium ion battery for a direct-current power supply and a preparation method thereof, wherein the preparation method comprises the following steps: respectively preparing a positive plate and a negative plate, and laminating the positive plate and the negative plate according to a set positive-negative capacity N/P ratio to obtain a battery core; injecting electrolyte into the battery core to obtain a manganese lithium ion battery for a direct-current power supply; the positive plate is prepared from a manganese material. The technical scheme provided by the invention has the advantages of simple preparation process, low requirement on the production environment of the battery, strong practicability and low production cost; compared with the traditional lithium ion battery systems, the manganese lithium ion battery provided by the invention has the advantage that the cost is obviously reduced.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a manganese lithium ion battery for a direct-current power supply and a preparation method thereof.
Background
With the development of future intelligent power grids, the requirements for new electric power equipment and stations including intelligent substations and the like are all compact, miniaturized, intelligent and multifunctional, and due to the defects of poor temperature characteristics, intolerance of overcharge and overdischarge, large maintenance workload and the like of the conventional lead-acid battery, the possibility of potential hazards existing in a direct-current system of the substation is gradually increased, and the modernization progress of the substation is hindered.
The lithium ion battery is used as a novel secondary power supply and has the advantages of high energy density, small self-discharge rate, no memory effect, long cycle life, various material systems, rapid technical progress and the like, so that the lithium ion battery has remarkable advantages and is a new trend for future development when replacing a lead-acid battery to become a storage battery of a direct-current system of a transformer substation.
At present, a direct-current power supply system still mainly uses a lead-acid battery, the lead-acid battery has the advantage of low battery cost, and a lithium ion battery needs to replace the lead-acid battery, and has low cost comparable to that of the lead-acid battery, safety characteristics of long-term high temperature resistance and overcharge resistance and good storage performance.
The requirements for the performance of the battery in the fields of 3C electronic products, electric vehicles and energy storage are high in cycle charging and discharging times, high in energy density and high in power, so that the requirements for the material characteristics and the production process of the battery are severe, and the cost of the battery is high. And the direct current power supply system of the transformer substation requires that the storage battery has good storage performance, and has low requirements on cycle charging and discharging times, energy density and power performance. If the power battery is directly applied to the transformer substation as the direct-current power supply storage battery, the requirements of the transformer substation on long service life and good storage performance of the floating charge storage battery cannot be met, excessive redundancy and waste of the battery in the aspects of cycle performance, energy density and power performance can be caused, and cost reduction is not facilitated. Therefore, there is a real need to develop low-cost lithium ion batteries that meet the performance requirements of substations.
Disclosure of Invention
The invention aims to provide a manganese lithium ion battery for a direct-current power supply and a preparation method thereof, which can meet the performance requirement of the direct-current power supply and improve the overall economy of a direct-current power supply system.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a manganese-based lithium ion battery for a direct current power supply, comprising:
respectively preparing a positive plate and a negative plate, and laminating the positive plate and the negative plate according to a set positive-negative capacity N/P ratio to obtain a battery core;
injecting electrolyte into the battery core to obtain a manganese lithium ion battery for a direct-current power supply;
the positive plate is prepared from a manganese material.
Further, the preparation of the positive plate comprises the following steps: obtaining a first active substance material, a first conductive agent, PVDF powder and NMP, and dissolving the PVDF in the NMP to form a glue solution; and uniformly stirring the glue solution, the first active material and the first conductive agent to obtain positive electrode slurry, vacuumizing, standing, coating, rolling, drying in vacuum, and storing in vacuum to obtain the positive electrode plate.
Further, the preparation of the negative plate comprises the following steps: obtaining a second active material, a second conductive agent and a binder; and uniformly stirring a second active material and a second conductive agent, adding a binder, uniformly stirring to obtain a negative electrode slurry, vacuumizing, standing, coating, rolling, vacuum drying, and performing vacuum storage to obtain the negative electrode plate.
Further, obtaining a first active material comprising: weighing Li according to the metering ratio of (2-4):12CO3And electrolytic MnO2And a compound containing a doping element, and reacting Li2CO3And electrolysis MnO2And mixing the compound containing the doping elements and the acetylene black ball mill, tabletting the precursor powder subjected to ball milling, putting the tabletted material into a muffle furnace for sintering, and naturally cooling to room temperature in the muffle furnace to obtain the first active substance material.
Further, among them, acetylene black accounts for Li2CO3And electrolytic MnO25 to 10 percent of the total mass of the compound containing the doping element and the acetylene black; the temperature for sintering in the muffle furnace is 600-900 ℃.
Furthermore, the positive ions of the compound containing the doping elements are one or more of Co, Al, Mg, Zn, Cr, Fe, Ni, Nb, La, Sm, Cu, Ti and Ge, and the negative ions are F, S, O, Cl, Se, I and PO4 3-One or more of them.
Further, the manganese-based material is a spinel manganese-based material or a manganese-based material with a layered structure.
Further, the manganese series material has a specific surface area ranging from 0.1 to 0.4m2/g。
Further, the second active material is a graphite material.
Further, the graphite material is artificial graphite or natural graphite, and the graphite particle granulation is primary granulation.
Furthermore, the mass ratio of the first active material to the first conductive agent to the PVDF powder is (90-93) to (3.5-5); the solid content of the anode slurry ranges from 50% to 70%;
the mass ratio of the second active material, the second conductive agent and the binder is (94-97): (1.5-3): 1.5-3); the solid content of the negative electrode slurry ranges from 50 to 70%.
Furthermore, the capacity N/P of the anode and the cathode is 1.0-1.5.
Further, the mass ratio of the first active material, the first conductive agent and the PVDF powder is 95: 5: 5; the solid content of the positive electrode slurry was 65%;
the mass ratio of the second active material to the second conductive agent to the binder is 96:2: 2; the solid content range of the cathode slurry is 55%;
the positive and negative electrode capacity N/P is 1.02.
A manganese-based lithium ion battery for a direct current power supply.
Compared with the prior art, the invention has the following beneficial effects:
1) the technical scheme provided by the invention has the advantages of simple preparation process, low requirement on the production environment of the battery, strong practicability and low production cost; compared with the traditional lithium ion battery systems, the manganese lithium ion battery provided by the invention has the advantages that the cost is obviously reduced by more than 30%; the lithium manganate material has rich raw material resources, low price and simple synthesis process, and the price of the lithium manganate anode material is only 2-3 ten thousand yuan/ton;
2) compared with the traditional lead-acid battery with a direct-current power supply, the charge-discharge efficiency of the manganese-based lithium-ion battery provided by the invention is improved by ten times, and the service life of the battery can be improved by more than 2 times compared with the traditional lead-acid battery after the material modification; the service life and the working efficiency are greatly improved, and the comprehensive cost performance is obviously improved;
3) the invention is different from the design concept that the traditional power lithium ion battery emphasizes the power performance and the long service life, the invention firstly develops the manganese lithium ion battery which is specially used for the direct-current power supply system, has the electrical performance and functional applicability and low cost, and meets the requirements of a transformer substation on the compactness, miniaturization and intelligent management of the direct-current power supply storage battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of a manufacturing process of a manganese-based lithium ion battery according to the present invention;
FIG. 2 is an SEM picture of lithium manganate particles granulated by the preparation method of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is exemplary in nature and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Referring to fig. 1, a process flow of the preparation process of the manganese-based lithium ion battery for the dc power supply of the present invention is the same as the conventional process flow, but the selection and addition ratio of the active material and the mixing manner in the slurry preparation process are different from those of the conventional coating process.
Example 1
The invention relates to a preparation method of a manganese-based lithium ion battery for a direct-current power supply, which comprises the following steps:
1) weighing a first active substance material, a first conductive agent and polyvinylidene fluoride (PVDF) powder according to the mass ratio of 90:5:5, wherein the first active substance material is a spinel lithium manganate material (the specific surface area is 0.1-0.4 m) with the mass of 2kg2(iv)/g); dissolving PVDF in N-methyl pyrrolidone (NMP) to form glue solution with mass concentration of 5%, adding the glue solution, active substance material and first conductive agent into a planetary stirring kettle, adjusting the solid content to 65% by deionized water, stirring for 3h, vacuumizing for 0.5h, standing, pouring the prepared slurry into a trough of a coating machine, adjusting the baking temperature of the coating machine to 90-95 ℃, and the running speed to be 2m/s, coating, finally rolling, and placing a pole piece roll in a vacuum oven for vacuum preservation at 90 ℃ to obtain the positive pole piece.
Wherein, the preparation process of the first active material comprises the following steps:
respectively weighing Li according to the metering ratio of 2:2:12CO3And electrolytic MnO2And Nb2O5And 5% acetylene black was added. Ball milling for 6 hours at the rotating speed of 350r/min, and ball millingThe precursor powder of (3) is tableted. And putting the pressed material into a muffle furnace for sintering at 600 ℃. And keeping the temperature for 6 hours to decompose the carbonate, and then naturally cooling the carbonate to room temperature in a muffle furnace to obtain the first active substance material.
2) Weighing a second active substance material, a second conductive agent and LA133 glue solution according to the mass ratio of 96:2:2, wherein the second active substance material is natural graphite with the mass of 1.5 kg; adding a second active substance material and a second conductive agent into a planetary stirring kettle, stirring for 2h for adjustment, adding a binder LA133 glue solution, stirring at a low speed for 0.5h, adjusting the solid content to 55% by using deionized water, vacuumizing for 0.5h, standing, pouring the prepared slurry into a trough of a coating machine, adjusting the baking temperature of the coating machine to 90-95 ℃, and the running speed to 2m/s, coating, finally rolling, and placing a pole piece roll in a vacuum oven for vacuum storage at 90 ℃ to obtain the negative pole piece.
3) Designing the N/P ratio of the positive and negative electrode capacities to be 1.02, and performing cell lamination on the prepared positive and negative electrode plates according to the proportion;
4) and binding and fixing the laminated cell, packaging to prepare a battery, pouring electrolyte, standing for 24h, and then carrying out 0.1C low-current formation to obtain the manganese lithium ion battery for the direct-current power supply.
The manganese lithium ion battery prepared by the embodiment has the cost reduced by more than 30 percent; compared with the traditional lead-acid battery with a direct-current power supply, the charging and discharging efficiency of the lead-acid battery is improved by ten times, and the service life of the lead-acid battery can be improved by more than 2 times compared with the traditional lead-acid battery after the material modification.
Example 2
The invention relates to a preparation method of a manganese-based lithium ion battery for a direct-current power supply, which comprises the following steps:
1) weighing a first active substance material, a first conductive agent and polyvinylidene fluoride (PVDF) powder according to the mass ratio of 92:4:4, wherein the first active substance material is a manganese material (the specific surface area is 0.1-0.4 m) with a layer structure and the mass of the manganese material is 2kg2(iv)/g); dissolving PVDF in N-methyl pyrrolidone (NMP) to form a glue solution with the mass concentration of 5%, and adding the glue solution, an active substance material and a first conductive agent into a planetary stirrerAnd (3) in a stirring kettle, adjusting the solid content to 50% by using deionized water, stirring for 3h, vacuumizing for 0.5h, standing, pouring the prepared slurry into a trough of a coating machine, adjusting the baking temperature of the coating machine to 90-95 ℃, keeping the speed at 2m/s, coating, finally rolling, and placing the pole piece roll in a vacuum oven for vacuum storage at 90 ℃ to obtain the positive pole piece.
Wherein, the preparation process of the first active material comprises the following steps:
respectively weighing Li according to the metering ratio of 2:2:12CO3Electrolytic MnO2And Nb2O5And 6% acetylene black was added. Ball milling is carried out for 6 hours at the rotating speed of 350r/min, and the ball-milled precursor powder is tabletted. And putting the pressed material into a muffle furnace for sintering at 700 ℃. And keeping the temperature for 6 hours to decompose the carbonate, and then naturally cooling the carbonate to room temperature in a muffle furnace to obtain the first active substance material.
2) Weighing a second active substance material, a second conductive agent and LA133 glue solution according to the mass ratio of 94:3:3, wherein the second active substance material is artificial graphite with the mass of 1.5 kg; adding a second active substance material and a second conductive agent into a planetary stirring kettle, stirring for 2h for adjustment, adding a binder LA133 glue solution, stirring at a low speed for 0.5h, adjusting the solid content to 50% by using deionized water, vacuumizing for 0.5h, standing, pouring the prepared slurry into a trough of a coating machine, adjusting the baking temperature of the coating machine to 90-95 ℃, and the running speed to 2m/s, coating, finally rolling, and placing a pole piece roll in a vacuum oven for vacuum storage at 90 ℃ to obtain the negative pole piece.
3) Designing the N/P ratio of the positive and negative electrode capacities to be 1, and performing cell lamination on the prepared positive and negative electrode plates according to the proportion;
4) and binding and fixing the laminated cell, packaging to prepare a battery, pouring electrolyte, standing for 24h, and then carrying out 0.1C low-current formation to obtain the manganese lithium ion battery for the direct-current power supply.
Example 3
The invention relates to a preparation method of a manganese-based lithium ion battery for a direct-current power supply, which comprises the following steps:
1) weighing a first active material according to the mass ratio of 93:3.5:3.5The conductive material comprises a material, a first conductive agent and polyvinylidene fluoride (PVDF) powder, wherein the first active material is a spinel lithium manganate material (the specific surface area is 0.1-0.4 m) with the mass of 2kg2(iv)/g); dissolving PVDF in N-methyl pyrrolidone (NMP) to form glue solution with mass concentration of 5%, adding the glue solution, active substance material and first conductive agent into a planetary stirring kettle, adjusting the solid content to 70% by using deionized water, stirring for 3h, vacuumizing for 0.5h, standing, pouring the prepared slurry into a trough of a coating machine, adjusting the baking temperature of the coating machine to 90-95 ℃, and the running speed to be 2m/s, coating, finally rolling, and placing a pole piece roll in a vacuum oven for vacuum storage at 90 ℃ to obtain the positive pole piece.
Wherein, the preparation process of the first active material comprises the following steps:
1) respectively weighing Li according to the metering ratio of 4:4:12CO3Electrolytic MnO2And Nb2O5And 8% of acetylene black was added. Ball milling is carried out for 6 hours at the rotating speed of 350r/min, and the ball-milled precursor powder is tabletted. And putting the pressed material into a muffle furnace for sintering at 700 ℃. And (4) keeping the temperature for 8h to decompose carbonate, and then naturally cooling to room temperature in a muffle furnace to obtain the first active substance material.
2) Weighing a second active substance material, a second conductive agent and LA133 glue solution according to the mass ratio of 97:1.5:1.5, wherein the second active substance material is natural graphite with the mass of 1.5 kg; adding a second active substance material and a second conductive agent into a planetary stirring kettle, stirring for 2h for adjustment, adding a binder LA133 glue solution, stirring at a low speed for 0.5h, adjusting the solid content to 70% by using deionized water, vacuumizing for 0.5h, standing, pouring the prepared slurry into a trough of a coating machine, adjusting the baking temperature of the coating machine to 90-95 ℃, and the running speed to 2m/s, coating, finally rolling, and placing a pole piece roll in a vacuum oven for vacuum storage at 90 ℃ to obtain the negative pole piece.
3) Designing the N/P ratio of the positive and negative electrode capacities to be 1.02, and performing cell lamination on the prepared positive and negative electrode plates according to the proportion;
4) and binding and fixing the laminated cell, packaging to prepare a battery, pouring electrolyte, standing for 24h, and then carrying out 0.1C low-current formation to obtain the manganese lithium ion battery for the direct-current power supply.
Example 4
The invention relates to a preparation method of a manganese-based lithium ion battery for a direct-current power supply, which comprises the following steps:
1) weighing a first active substance material, a first conductive agent and polyvinylidene fluoride (PVDF) powder according to the mass ratio of 92:5:3, wherein the first active substance material is a spinel lithium manganate material (the specific surface area is 0.1-0.4 m) with the mass of 2kg2(iv)/g); dissolving PVDF in N-methyl pyrrolidone (NMP) to form glue solution with mass concentration of 5%, adding the glue solution, active substance material and first conductive agent into a planetary stirring kettle, adjusting the solid content to 60% by using deionized water, stirring for 3h, vacuumizing for 0.5h, standing, pouring the prepared slurry into a trough of a coating machine, adjusting the baking temperature of the coating machine to 90-95 ℃, and the running speed to be 2m/s, coating, finally rolling, and placing a pole piece roll in a vacuum oven for vacuum storage at 90 ℃ to obtain the positive pole piece.
Wherein, the preparation process of the first active material comprises the following steps:
1) respectively weighing Li according to the metering ratio of 2:2:12CO3Electrolytic MnO2And Nb2O5And 10% acetylene black was added. Ball milling is carried out for 6 hours at the rotating speed of 350r/min, and the ball-milled precursor powder is tabletted. And putting the pressed material into a muffle furnace for sintering at 900 ℃. And (4) keeping the temperature for 10 hours to decompose carbonate, and then naturally cooling to room temperature in a muffle furnace to obtain the first active substance material.
2) Weighing a second active substance material, a second conductive agent and LA133 glue solution according to the mass ratio of 95:2:3, wherein the second active substance material is artificial graphite with the mass of 1.5 kg; adding a second active substance material and a second conductive agent into a planetary stirring kettle, stirring for 2h for adjustment, adding a binder LA133 glue solution, stirring at a low speed for 0.5h, adjusting the solid content to 65% by using deionized water, vacuumizing for 0.5h, standing, pouring the prepared slurry into a trough of a coating machine, adjusting the baking temperature of the coating machine to be 90-95 ℃, and the running speed to be 2m/s, coating, finally rolling, and placing a pole piece roll in a vacuum oven for vacuum storage at 90 ℃ to obtain the negative pole piece.
3) Designing the N/P ratio of the positive and negative electrode capacities to be 1.02, and performing cell lamination on the prepared positive and negative electrode plates according to the proportion;
4) and binding and fixing the laminated cell, packaging to prepare a battery, pouring electrolyte, standing for 24h, and then carrying out 0.1C low-current formation to obtain the manganese lithium ion battery for the direct-current power supply.
As can be seen from fig. 2, the first active material particles prepared by the process for preparing the first active material of example 1 have smooth surfaces, are subjected to primary granulation, reduce the cost of secondary granulation, have an average particle size of more than 10 μm, have a low specific surface area, and can greatly reduce the dosage of NMP (NMP) used as a solvent during homogenization.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (6)
1. A method for preparing a manganese-based lithium ion battery for a direct current power supply, comprising:
respectively preparing a positive plate and a negative plate, and laminating the positive plate and the negative plate according to a set positive-negative capacity N/P ratio to obtain a battery core;
injecting electrolyte into the battery core to obtain a manganese lithium ion battery for a direct-current power supply;
the positive plate is prepared from a manganese material;
preparing a positive plate, comprising:
obtaining a first active material, a first conductive agent, PVDF powder and NMP;
dissolving PVDF in NMP to form a glue solution;
uniformly stirring the glue solution, a first active material and a first conductive agent to obtain positive electrode slurry, vacuumizing, standing, coating, rolling, vacuum drying and then vacuum storing to obtain a positive plate;
the mass ratio of the first active material to the first conductive agent to the PVDF powder is (90-93): (3.5-5): (3.5-5); the solid content of the anode slurry ranges from 50% to 70%;
the first active material is a manganese-based material; the manganese series material is a spinel manganese series material or a manganese series material with a layered structure;
obtaining a first active material comprising:
weighing Li according to the metering ratio of (2-4):12CO3And electrolytic MnO2And a compound containing a doping element, and reacting Li2CO3And electrolytic MnO2Mixing the compound containing the doping elements and acetylene black by a ball mill, tabletting the precursor powder subjected to ball milling, putting the tabletted material into a muffle furnace for sintering, and naturally cooling to room temperature in the muffle furnace to obtain a first active substance material;
wherein the acetylene black is Li2CO3And electrolytic MnO25 to 10 percent of the total mass of the compound containing the doping element and the acetylene black; the sintering temperature in the muffle furnace is 600-900 ℃;
the positive ions of the compound containing the doping elements are one or more of Co, Al, Mg, Zn, Cr, Fe, Ni, Nb, La, Sm, Cu, Ti and Ge, and the negative ions are one or more of F, S, O, Cl, Se and I.
2. The preparation method according to claim 1, wherein preparing the negative electrode sheet comprises:
obtaining a second active material, a second conductive agent and a binder;
and uniformly stirring a second active material and a second conductive agent, adding a binder, uniformly stirring to obtain a negative electrode slurry, vacuumizing, standing, coating, rolling, vacuum drying, and performing vacuum storage to obtain the negative electrode plate.
3. The method according to claim 2, wherein the manganese-based material has a specific surface area in the range of 0.1 to 0.4m2/g。
4. The method of claim 1, wherein the second active material is a graphite material.
5. The method according to claim 1, wherein the positive-negative electrode capacity N/P is 1.0 to 1.5.
6. A manganese-based lithium ion battery for a direct current power supply, characterized by being prepared by the method of any one of claims 1 to 5.
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CN104600273A (en) * | 2013-10-30 | 2015-05-06 | 北京有色金属研究总院 | Phosphorus-containing lithium ion battery anode material and preparation method thereof |
CN104852052A (en) * | 2014-02-18 | 2015-08-19 | 北京有色金属研究总院 | A lithium-rich positive electrode material, a preparing method thereof, a lithium ion battery positive electrode containing the positive electrode material, and a lithium ion battery |
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CN104600273A (en) * | 2013-10-30 | 2015-05-06 | 北京有色金属研究总院 | Phosphorus-containing lithium ion battery anode material and preparation method thereof |
CN104852052A (en) * | 2014-02-18 | 2015-08-19 | 北京有色金属研究总院 | A lithium-rich positive electrode material, a preparing method thereof, a lithium ion battery positive electrode containing the positive electrode material, and a lithium ion battery |
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