CN109088052B - Tin composite lithium electrode, preparation method thereof and battery comprising same - Google Patents
Tin composite lithium electrode, preparation method thereof and battery comprising same Download PDFInfo
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- CN109088052B CN109088052B CN201810870071.5A CN201810870071A CN109088052B CN 109088052 B CN109088052 B CN 109088052B CN 201810870071 A CN201810870071 A CN 201810870071A CN 109088052 B CN109088052 B CN 109088052B
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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
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/626—Metals
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
Abstract
The invention belongs to the technical field of metal lithium batteries, and particularly relates to a tin composite lithium electrode, a preparation method thereof and a battery comprising the tin composite lithium electrode, wherein the tin composite lithium electrode comprises a metal lithium sheet and a tin powder layer sprayed on the metal lithium sheet, the thickness of the metal lithium sheet is 10-100 mu m, and the thickness of the tin powder layer is less than 10 mu m; the preparation method of the tin composite lithium electrode comprises the steps of spraying baked and dried tin powder on a metal lithium sheet in a dry environment and rolling; the battery uses a tin composite lithium electrode as a negative electrode. Compared with the prior art, the invention improves the conduction rate of lithium ions, inhibits the growth of lithium dendrites and improves the cycle performance and the safety performance of the battery.
Description
Technical Field
The invention belongs to the technical field of metal lithium batteries, and particularly relates to a tin composite lithium electrode, a preparation method of the tin composite lithium electrode and a battery comprising the tin composite lithium electrode.
Background
With the continuous update and development of lithium battery technology, the advantages of light weight, high capacity and long service life are gradually favored by consumers. In recent years, lithium batteries have been widely used not only in portable electronic devices but also in large and medium-sized electric devices such as electric vehicles, electric bicycles, and electric tools because of their advantages such as high voltage, large cycle times, and long storage time.
With the popularization of mobile internet devices such as smart phones and notebook computers, the popularization of electric vehicles such as electric bicycles and electric motorcycles, and the development of aerospace technologies such as unmanned aerial vehicles and space detectors, the performance of lithium ion batteries face higher development requirements, and high energy density has become one of the research directions of high-performance lithium ion batteries.
In order to improve the energy density of the lithium ion battery, the key point is to search for a high-capacity positive and negative electrode active material. The theoretical specific capacity of the metallic lithium cathode is 3860mAh/g, the voltage platform is-3.04V (vs standard hydrogen electrode), and the metallic lithium cathode has excellent conductivity and is very suitable for being used as the cathode of a high-energy-density lithium ion battery. However, when the lithium metal negative electrode is charged, lithium ions are gathered to expand, and the expansion is uneven, which causes pits and cracks, so that the lithium ions overflow from the cracks to form moss-like growth, i.e., lithium dendrites. This may cause a short circuit of the battery, which may affect the safety of the battery, and the precipitation of lithium ions may cause a decrease in the performance of the battery, which may shorten the service life of the battery.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the tin composite lithium electrode is provided, the conduction rate of lithium ions is improved, and the growth of lithium dendrites is inhibited.
The second purpose of the invention is: a method for preparing a tin composite lithium electrode is provided.
The third purpose of the invention is that: a battery including a tin composite lithium electrode is provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a tin composite lithium electrode, includes metal lithium piece and spray coating in tin bisque on the metal lithium piece, the thickness of metal lithium piece is 10 ~ 100 mu m, the thickness on tin bisque is less than 10 mu m.
As an improvement of the tin composite lithium electrode, the particle size of tin powder in the tin powder layer is 1 nm-50 mu m.
A preparation method of a tin composite lithium electrode comprises the following steps:
firstly, preparing a metal lithium sheet and tin powder with the particle size of 1 nm-50 mu m, and then carrying out vacuum baking on the tin powder to obtain dry tin powder;
step two, under a dry environment, uniformly spraying dry tin powder on the surface of the metal lithium sheet by using spraying equipment to obtain the metal lithium sheet with the surface sprayed with the tin powder layer;
and thirdly, rolling the metal lithium sheet with the tin powder layer sprayed on the surface by using a rolling machine in a dry environment to obtain the tin composite lithium electrode.
As an improvement of the preparation method of the tin composite lithium electrode, in the step I, the temperature of vacuum baking is 60-200 ℃, and the vacuum degree is less than or equal to-90 KPa.
As an improvement of the preparation method of the tin composite lithium electrode, in the second step and the third step, the drying environment is that the dew point does not exceed minus 35 ℃.
In the third step, the thickness of the rolled metal lithium sheet is 10-100 μm.
In the third step, the thickness of the rolled tin powder layer is less than 10 μm.
A battery comprising a tin complex lithium electrode comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode at an interval, and an electrolyte, wherein the negative electrode is the tin complex lithium electrode described above.
As an improvement of the battery including the tin-lithium composite lithium electrode according to the present invention, the active material of the positive electrode includes at least one of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate, lithium iron phosphate, a nickel manganese binary material, and lithium nickel cobalt aluminate.
The invention has the beneficial effects that: the invention provides a tin composite lithium electrode, a preparation method thereof and a battery comprising the electrode, wherein tin and lithium are compounded, tin is always in a lithium-rich state due to the close contact of tin and lithium, so that severe volume expansion is avoided, the diffusion speed of Li in Sn is very high, and the potential difference of Li in the process of embedding and removing in Sn is lower than 500mV, which is beneficial to rapidly penetrating through an Sn layer to be diffused into a Li metal cathode, so that lithium ions can be rapidly conducted in Sn, the aim of inhibiting the growth of lithium dendrites of the metal lithium cathode is fulfilled, and the cycle performance and the safety performance of the metal lithium battery are improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Comparative example
A metal lithium sheet with the thickness of 50 mu m is taken as a negative electrode, and a positive electrode, electrolyte and a diaphragm which are the same as those in the embodiment are adopted to obtain a naked battery cell through lamination or winding. And placing the bare cell in an outer package, injecting electrolyte into the dried battery, packaging, standing, forming, shaping, grading and finishing the preparation of the battery.
Example 1
The embodiment provides a tin composite lithium electrode, which comprises a metal lithium sheet and a tin powder layer sprayed on the metal lithium sheet, wherein the thickness of the metal lithium sheet is 10 micrometers, and the thickness of the tin powder layer is 3 micrometers. The grain diameter of tin powder in the tin powder layer is 1 nm-50 mu m, and the preparation method comprises the following steps:
firstly, preparing a metal lithium sheet and tin powder with the particle size of 1 nm-50 mu m, and then carrying out vacuum baking on the tin powder to obtain dry tin powder; the temperature of vacuum baking is 60-200 ℃, and the vacuum degree is less than or equal to-90 KPa;
step two, uniformly spraying dry tin powder on the surface of the metal lithium sheet by using spraying equipment in a dry environment (the dew point does not exceed-35 ℃) to obtain the metal lithium sheet with the tin powder layer sprayed on the surface;
and thirdly, rolling the metal lithium sheet with the tin powder layer sprayed on the surface by using a roller press in a dry environment (the dew point does not exceed-35 ℃) to obtain the tin composite lithium electrode.
Example 2
The difference from example 1 is: in this example, the thickness of the lithium metal sheet is 30 μm, and the thickness of the tin powder layer is 5 μm.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is: in this example, the thickness of the lithium metal sheet was 50 μm, and the thickness of the tin powder layer was 6 μm.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is: in this example, the thickness of the lithium metal sheet was 80 μm, and the thickness of the tin powder layer was 7.5 μm.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is: in this example, the thickness of the lithium metal sheet was 100 μm and the thickness of the tin powder layer was 9 μm.
The rest is the same as embodiment 1, and the description is omitted here.
Taking the tin composite lithium battery prepared in the embodiment 1-5 as a battery negative electrode, matching with a positive electrode (active substance is at least one of lithium cobaltate, lithium manganate, lithium nickel cobalt manganese, lithium iron phosphate, nickel manganese binary material and lithium nickel cobalt aluminate) and a diaphragm, stacking in sequence, enabling the diaphragm to be positioned between the positive electrode and the negative electrode, and winding to obtain a bare cell; and placing the bare cell in an outer package, injecting the prepared electrolyte into the dried battery, packaging, standing, forming, shaping and grading to finish the preparation of the battery. The following performance tests were performed on the prepared batteries:
1) and (3) testing the normal-temperature cycle performance: at 25 ℃, the batteries after capacity grading are charged to 4.20V at constant current and constant voltage of 0.2C, the current is cut off at 0.02C, then the batteries are discharged to 3.0V at constant current of 0.5C, the discharge capacity of the batteries is measured, and the capacity retention rate of the 500 th cycle is calculated after the batteries are cycled according to the cycle and are charged/discharged for 500 times.
2) High temperature 45 ℃ cycle performance test: at 45 ℃, the battery after capacity grading is charged to 4.20V at constant current and constant voltage according to 0.2C, the current is cut off to 0.02C, then the battery is discharged to 3.0V at constant current according to 0.5C, the discharge capacity and the internal resistance of the battery are measured, and the 500 th cycle capacity retention rate and the internal resistance change rate are calculated after the battery is cycled according to the cycle and is charged/discharged for 500 cycles.
3) And (4) safety performance testing: performing a puncture experiment and an impact experiment on the battery which is cycled for 100 times at 25 ℃, wherein the puncture experiment is to use a nail to penetrate through the center of the battery after the battery is fully charged, leave the nail in the battery and observe the condition of the battery; in the impact test, after the battery is fully charged, a hard rod is placed on the battery, and a heavy object is used for smashing the hard rod from the upper air to observe the condition of the battery.
The results of the above performance tests are detailed in table 1.
Table 1 results of performance testing
As can be seen from the above table, the cycle performance and safety performance of the battery prepared from the tin composite lithium electrode of examples 1 to 5 are superior to those of the battery prepared in comparative example 1, because tin and lithium metal are compounded in the invention, and tin is in close contact with lithium, so that not only is tin always in a lithium-rich state and severe volume expansion avoided, but also lithium ions can be rapidly conducted in Sn, and the purpose of inhibiting the growth of lithium dendrites of a lithium metal cathode is achieved, thereby effectively improving the cycle performance and safety performance of the battery.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (8)
1. A tin composite lithium electrode is characterized in that: the tin powder coating comprises a metal lithium sheet and a tin powder layer sprayed on the metal lithium sheet, wherein the thickness of the metal lithium sheet is 50 mu m, and the thickness of the tin powder layer is 6 mu m, or the thickness of the metal lithium sheet is 100 mu m, and the thickness of the tin powder layer is 9 mu m; the particle size of tin powder in the tin powder layer is 1 nm-50 mu m.
2. A method for preparing the tin composite lithium electrode of claim 1, comprising the steps of:
firstly, preparing a metal lithium sheet and tin powder with the particle size of 1 nm-50 mu m, and then carrying out vacuum baking on the tin powder to obtain dry tin powder;
step two, under a dry environment, uniformly spraying dry tin powder on the surface of the metal lithium sheet by using spraying equipment to obtain the metal lithium sheet with the surface sprayed with the tin powder layer;
and thirdly, rolling the metal lithium sheet with the tin powder layer sprayed on the surface by using a rolling machine in a dry environment to obtain the tin composite lithium electrode.
3. The method for producing a tin composite lithium electrode according to claim 2, characterized in that: in the first step, the temperature of vacuum baking is 60-200 ℃, and the vacuum degree is less than or equal to-90 KPa.
4. The method for producing a tin composite lithium electrode according to claim 2, characterized in that: in steps two and three, the drying environment is such that the dew point does not exceed-35 ℃.
5. The method for producing a tin composite lithium electrode according to claim 2, characterized in that: in step three, the thickness of the lithium metal sheet is 50 μm and the thickness of the tin powder layer is 6 μm.
6. The method for producing a tin composite lithium electrode according to claim 2, characterized in that: in step three, the thickness of the lithium metal sheet is 100 μm and the thickness of the tin powder layer is 9 μm.
7. The utility model provides a battery that contains compound lithium electrode of tin, includes anodal, negative pole, interval set up in diaphragm and electrolyte between anodal and the negative pole, its characterized in that: the negative electrode is the tin composite lithium electrode according to claim 1.
8. The battery comprising a tin-composite lithium electrode according to claim 7, wherein: the active substance of the positive electrode comprises at least one of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate, lithium iron phosphate, nickel manganese binary material and lithium nickel cobalt aluminate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810870071.5A CN109088052B (en) | 2018-08-02 | 2018-08-02 | Tin composite lithium electrode, preparation method thereof and battery comprising same |
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| CN201810870071.5A CN109088052B (en) | 2018-08-02 | 2018-08-02 | Tin composite lithium electrode, preparation method thereof and battery comprising same |
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| CN109088052A CN109088052A (en) | 2018-12-25 |
| CN109088052B true CN109088052B (en) | 2021-10-15 |
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| CN112436140A (en) * | 2019-08-26 | 2021-03-02 | 青岛九环新越新能源科技股份有限公司 | Composite material for inhibiting dendritic crystal growth |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415123A (en) * | 1999-11-23 | 2003-04-30 | 分子技术股份有限公司 | Lithium anodes for electrochemical cells |
| WO2005089352A2 (en) * | 2004-03-16 | 2005-09-29 | Toyota Technical Canter Usa, Inc. | Battery with molten salt electrolyte and protected lithium-based negative electrode material |
| CN106702370A (en) * | 2017-01-05 | 2017-05-24 | 滁州市友邦涂装有限公司 | Metal powder spraying technique for improving spraying quality of workpiece |
| WO2017140649A1 (en) * | 2016-02-19 | 2017-08-24 | Solvay Specialty Polymers Italy S.P.A. | Multilayer assembly |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100450208B1 (en) * | 2002-09-23 | 2004-09-24 | 삼성에스디아이 주식회사 | Negative electrode for lithium battery and lithium battery comprising same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415123A (en) * | 1999-11-23 | 2003-04-30 | 分子技术股份有限公司 | Lithium anodes for electrochemical cells |
| WO2005089352A2 (en) * | 2004-03-16 | 2005-09-29 | Toyota Technical Canter Usa, Inc. | Battery with molten salt electrolyte and protected lithium-based negative electrode material |
| WO2017140649A1 (en) * | 2016-02-19 | 2017-08-24 | Solvay Specialty Polymers Italy S.P.A. | Multilayer assembly |
| CN106702370A (en) * | 2017-01-05 | 2017-05-24 | 滁州市友邦涂装有限公司 | Metal powder spraying technique for improving spraying quality of workpiece |
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Denomination of invention: Tin composite lithium electrode and its preparation method, as well as battery containing the electrode Effective date of registration: 20230829 Granted publication date: 20211015 Pledgee: Agricultural Bank of China Limited Zhuzhou branch Pledgor: HUNAN LIFANG NEW ENERGY SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2023980054119 |