CN113506869A - Lithium battery and anode thereof - Google Patents
Lithium battery and anode thereof Download PDFInfo
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- CN113506869A CN113506869A CN202110494723.1A CN202110494723A CN113506869A CN 113506869 A CN113506869 A CN 113506869A CN 202110494723 A CN202110494723 A CN 202110494723A CN 113506869 A CN113506869 A CN 113506869A
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- strontium salt
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
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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
- H01M4/139—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
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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
- H01M4/48—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
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- 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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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium battery, comprising: the electrolyte and the diaphragm are arranged between the anode and the cathode, the anode comprises soluble strontium salt, and the mass ratio of the soluble strontium salt to the anode is 0.1-1%. The soluble strontium salt is used for supplementing strontium ions in a strontium cobaltate structure, so that the energy density of the lithium battery is high.
Description
Technical Field
The present invention relates to a lithium battery and a positive electrode thereof, and more particularly, to a strontium-doped lithium battery and a positive electrode thereof.
Background
At present, with the rapid development of the global new energy automobile industry, the new energy industry is also developed vigorously. From the current domestic new energy automobile industry, the development of electric vehicles is a necessary trend of environmental protection and industry upgrading. With the sales volume of electric automobiles becoming larger and larger, the demand of power batteries also becomes larger and larger, and meanwhile, higher requirements are put on the capacity, voltage and service life of the power batteries.
The energy density of the lithium battery depends on the specific capacity of the anode to a great extent, and the specific capacity of mainstream anode materials supplied in the current market is less than 280mAh/g, so that the high energy density requirement of the current market can not be met. Although the specific capacity of some positive electrode materials is higher than 280mAh/g, the process is complex, the production cost is high, and large-scale mass production is difficult.
Disclosure of Invention
The embodiment of the invention aims to provide a lithium battery and a positive electrode thereof, which are used for solving the problem that the existing lithium battery is low in energy density.
The embodiment of the invention discloses a lithium battery, which comprises: the electrolyte and the diaphragm are arranged between the anode and the cathode, the anode comprises soluble strontium salt, and the mass ratio of the soluble strontium salt to the anode is 0.1-1%.
Preferably, the soluble strontium salt is added after the positive electrode is manufactured, or a part of the soluble strontium salt is residual in the manufacturing process of the positive electrode, and a part of the soluble strontium salt is detected and added after the positive electrode is manufactured.
Preferably, the soluble strontium salt comprises: one or more of strontium nitrate, strontium chloride, strontium perchlorate, strontium bicarbonate, strontium chlorate, strontium bromide and strontium iodide.
Preferably, the electrolyte comprises one or more of sodium chloride, potassium chloride or calcium chloride, and the soluble strontium salt is strontium chloride.
Preferably, the positive electrode manufacturing step includes:
s1: uniformly stirring lithium nickel cobaltate, lithium cobalt oxide and a soluble strontium salt solution;
s2: the lithium nickel cobaltate and lithium cobalt oxide stirred with the soluble strontium salt solution were calcined.
Preferably, the mass ratio of the strontium salt in the soluble strontium salt solution to the lithium nickel cobaltate and the lithium cobalt oxide is 1: 9-2: 8.
preferably, the calcination temperature is 650-900 ℃, and the calcination time is 2-12 hours.
The embodiment of the invention also discloses a lithium battery anode, which comprises: lithium nickel cobaltate and lithium cobalt oxide, further comprising: the mass ratio of the soluble strontium salt to the anode is 0.1-1%.
Preferably, the soluble strontium salt is added after the positive electrode is manufactured, or a part of the soluble strontium salt is residual in the manufacturing process of the positive electrode, and a part of the soluble strontium salt is detected and added after the positive electrode is manufactured.
Preferably, the positive electrode manufacturing step includes:
s1: uniformly stirring lithium nickel cobaltate, lithium cobalt oxide and a soluble strontium salt solution;
s2: the lithium nickel cobaltate and lithium cobalt oxide stirred with the soluble strontium salt solution were calcined.
The lithium battery and the anode thereof disclosed by the embodiment of the invention further comprise: the mass ratio of the soluble strontium salt to the anode is 0.1-1%, and the soluble strontium salt is used for supplementing strontium ions in a strontium cobaltate structure, so that the energy density of the lithium battery is high.
Drawings
Fig. 1 is a schematic structural diagram of a lithium battery according to an embodiment of the present invention;
fig. 2 is a schematic view of a method for manufacturing a positive electrode material for a lithium battery according to another embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Fig. 1 is a schematic diagram of a lithium battery according to an embodiment of the present invention. The lithium battery 10 includes: a positive electrode 11, a negative electrode 12, an electrolyte 13, and a separator 14, the electrolyte 13 and the separator 14 being interposed between the positive electrode 11 and the negative electrode 12. The electrolyte 13 is further dispersed in the gap of the positive electrode 11. The lithium battery 10 further comprises a first current collector 18 and a second current collector 19, wherein the first current collector 18 is used for collecting the current of the anode 11, and the second current collector 19 is used for collecting the current of the cathode 12. The positive electrode 11, the negative electrode 12, the electrolyte 13, the separator 14, the first current collector 18, and the second current collector 19 are all hermetically placed in a case (not shown).
The mass ratio of the lithium nickel cobaltate to the lithium cobalt oxide in the positive electrode 11 is 1:1, the positive electrode 11 comprises a lithium nickel cobaltate layer and a lithium cobalt oxide layer, the lithium cobalt oxide is sprayed on the surface of the lithium nickel cobaltate, and the lithium cobalt oxide layer is arranged between the lithium nickel cobaltate layer and the diaphragm 14 and used for improving the corrosion resistance, high temperature resistance, oxidation resistance and other characteristics of the lithium nickel cobaltate layer, the service life of the battery can be greatly prolonged, and the upper limit of charging current is obviously improved.
The anode 11 further comprises a soluble strontium salt, and the mass ratio of the soluble strontium salt to the anode is 0.1-1%. The soluble strontium salt comprises: one or more of strontium nitrate, strontium chloride, strontium perchlorate, strontium bicarbonate, strontium chlorate, strontium bromide and strontium iodide. The soluble strontium salt is added after the anode is manufactured, or part of the soluble strontium salt is residual in the manufacturing process of the anode, and part of the soluble strontium salt is added after the anode is manufactured and detected. The added soluble strontium salt is used for supplementing strontium ions in the strontium cobaltate structure, and when part of the strontium cobaltate coating layer is damaged or broken, the strontium salt provides strontium ions for timely supplementing, so that the ionic conductivity of the damaged or broken part is compensated.
When the soluble strontium salt is required to be added after the anode is manufactured, the soluble strontium salt solution is uniformly sprayed on the surface of the anode after the anode is manufactured and before the next procedure is carried out. The process can ensure that the strontium salt is locally concentrated in the lithium battery structure and has higher local concentration, and is favorable for timely repairing the damaged strontium cobaltate coating layer.
The manufacturing steps of the anode comprise: s1: the lithium nickel cobaltate and lithium cobalt oxide are evenly stirred with the soluble strontium salt solution. The solvent is deionized water, and the mass ratio of strontium salt in the soluble strontium salt solution to lithium nickel cobaltate and lithium cobalt oxide is 1: 9-2: and 8, because the strontium salt is dissolved in water, the strontium salt can be conveniently and fully contacted with the lithium nickel cobaltate and the lithium cobalt oxide, the process is simple and uniformly distributed, and the manufacturing process is obviously superior to other solid strontium salt processes. S2: the lithium nickel cobaltate and lithium cobalt oxide stirred with the soluble strontium salt solution were calcined. The calcining temperature is 650-900 ℃, and the calcining time is 2-12 hours. Preferably, the calcination is carried out in a nitrogen environment, and the temperature rising speed of the calcination is 10-20 ℃/min. Through this calcination, the coating that contains strontium cobaltate has been formed on the surface of lithium nickel cobaltate and lithium cobalt oxide granule, and this coating has ionic conductivity height, the good advantage of thermal stability, and the density of this coating is higher, can further promote anodal energy density.
The cathode 12 comprises one or a combination of more than two of a carbon cathode material, a silicon-based cathode material, a tin-based cathode material and a nano cathode material.
The electrolyte 13 contains one or a combination of two or more of sodium chloride, potassium chloride, and calcium chloride. Preferably, the soluble strontium salt is strontium chloride. At this time, the negative ions in the lithium battery 10 are all chloride ions, so that other secondary chemical reactions can be effectively avoided.
The diaphragm 14 is a polymer diaphragm, the polymer diaphragm is a porous structure, the porous structure is a through hole, and preferably, the through hole is a zigzag through hole.
Fig. 2 is a schematic diagram illustrating a method for manufacturing a positive electrode material for a lithium battery according to another embodiment of the present invention. A method for manufacturing a lithium battery positive electrode includes the steps of:
s1: uniformly stirring lithium nickel cobaltate, lithium cobalt oxide and a soluble strontium salt solution;
s2: the lithium nickel cobaltate and lithium cobalt oxide stirred with the soluble strontium salt solution were calcined.
The solvent of the soluble strontium salt solution is deionized water, and the mass ratio of strontium salt in the soluble strontium salt solution to lithium nickel cobaltate to lithium cobalt oxide is 1: 9-2: and 8, because the strontium salt is dissolved in water, the strontium salt can be conveniently and fully contacted with the lithium nickel cobaltate and the lithium cobalt oxide, the process is simple and uniformly distributed, and the manufacturing process is obviously superior to other solid strontium salt processes. S2: the lithium nickel cobaltate and lithium cobalt oxide stirred with the soluble strontium salt solution were calcined. The calcining temperature is 650-900 ℃, and the calcining time is 2-12 hours. Preferably, the calcination is carried out in a nitrogen environment, and the temperature rising speed of the calcination is 10-20 ℃/min. Through this calcination, the coating that contains strontium cobaltate has been formed on the surface of lithium nickel cobaltate and lithium cobalt oxide granule, and this coating has ionic conductivity height, the good advantage of thermal stability, and the density of this coating is higher, can further promote anodal energy density.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
Claims (10)
1. A lithium battery, comprising: a positive electrode, a negative electrode, an electrolyte and a separator, the electrolyte and the separator being interposed between the positive electrode and the negative electrode, characterized in that: the anode comprises a soluble strontium salt, and the mass ratio of the soluble strontium salt to the anode is 0.1-1%.
2. A lithium battery as claimed in claim 1, characterized in that: the soluble strontium salt is added after the anode is manufactured, or part of the soluble strontium salt is residual in the manufacturing process of the anode, and part of the soluble strontium salt is added after the anode is manufactured and detected.
3. A lithium battery as claimed in claim 1 or 2, characterized in that: the soluble strontium salt comprises: one or more of strontium nitrate, strontium chloride, strontium perchlorate, strontium bicarbonate, strontium chlorate, strontium bromide and strontium iodide.
4. A lithium battery as claimed in claim 1, characterized in that: the electrolyte comprises one or the combination of more than two of sodium chloride, potassium chloride or calcium chloride, and the soluble strontium salt is strontium chloride.
5. A lithium battery as claimed in claim 1, characterized in that: the manufacturing steps of the anode comprise:
s1: uniformly stirring lithium nickel cobaltate, lithium cobalt oxide and a soluble strontium salt solution;
s2: the lithium nickel cobaltate and lithium cobalt oxide stirred with the soluble strontium salt solution were calcined.
6. A lithium battery as claimed in claim 5, characterized in that: the mass ratio of the strontium salt in the soluble strontium salt solution to the lithium nickel cobaltate and the lithium cobalt oxide is 1: 9-2: 8.
7. a lithium battery as claimed in claim 1, characterized in that: the calcining temperature is 650-900 ℃, and the calcining time is 2-12 hours.
8. A lithium battery positive electrode comprising: lithium nickel cobaltate and lithium cobalt oxide characterized by further comprising: the mass ratio of the soluble strontium salt to the anode is 0.1-1%.
9. The positive electrode for lithium batteries according to claim 8, wherein: the soluble strontium salt is added after the anode is manufactured, or part of the soluble strontium salt is residual in the manufacturing process of the anode, and part of the soluble strontium salt is added after the anode is manufactured and detected.
10. The positive electrode for lithium batteries according to claim 8, wherein: the manufacturing steps of the anode comprise:
s1: uniformly stirring lithium nickel cobaltate, lithium cobalt oxide and a soluble strontium salt solution;
s2: the lithium nickel cobaltate and lithium cobalt oxide stirred with the soluble strontium salt solution were calcined.
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| CN202110494723.1A CN113506869A (en) | 2021-05-07 | 2021-05-07 | Lithium battery and anode thereof |
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| CN202110494723.1A CN113506869A (en) | 2021-05-07 | 2021-05-07 | Lithium battery and anode thereof |
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Application publication date: 20211015 |