CN111403687A - Lithium metal cathode, preparation method and lithium ion battery - Google Patents
Lithium metal cathode, preparation method and lithium ion battery Download PDFInfo
- Publication number
- CN111403687A CN111403687A CN202010228963.2A CN202010228963A CN111403687A CN 111403687 A CN111403687 A CN 111403687A CN 202010228963 A CN202010228963 A CN 202010228963A CN 111403687 A CN111403687 A CN 111403687A
- Authority
- CN
- China
- Prior art keywords
- lithium metal
- negative electrode
- lithium
- reaction substrate
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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
- H01M4/13—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium metal negative electrode which comprises a substrate and a surface layer formed on the substrate, wherein the substrate and the surface layer are both made of lithium metal or lithium alloy, a plurality of holes are formed in the surface layer, and the holes are communicated with each other to form a three-dimensional network structure. The lithium metal negative electrode has a high lithium affinity. The invention also provides a preparation method of the lithium metal cathode and a lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium metal cathode, a preparation method of the lithium metal cathode and a lithium ion battery.
Background
The development of 3C electronic devices and electric vehicles has put higher and higher demands on secondary batteries, and current commercialized lithium ion battery systems have approached the energy utilization limit, and it is difficult to further increase the energy density by a large margin through process or device optimization, and there is a need for electrodes and materials with higher energy density.
The lithium metal negative electrode has higher theoretical specific capacity (3860mAh g)-1) And the cathode potential is lower (-3.04V), so that the cathode can be used as an ideal cathode of a metal ion battery with the highest theoretical energy density, and has great development potential. However, lithium metal negative electrodes are not yet commercially available because lithium dendrites are easily formed during charging and discharging to cause short-circuiting of batteries, and the breakage of the Solid Electrolyte Interface (SEI) on the surface thereof causes problems such as consumption of electrolyte and low coulombic efficiency.
The three-dimensional current collector can reduce the effective current density by improving the specific surface area and inhibit the formation of lithium dendrites, and is an important solution for solving the difficult problem of the lithium metal negative electrode. However, the existing three-dimensional current collectors (such as foamed nickel/copper and the like) have high quality, the energy density of the battery can be reduced when the current collectors are used, the lithium affinity of materials such as nickel/copper and the like is insufficient, and the lithium deposition appearance is not ideal.
Disclosure of Invention
In view of the above, it is desirable to provide a lithium metal negative electrode having a surface three-dimensional structure, which has a high lithium affinity.
In addition, a preparation method of the lithium metal negative electrode is also needed.
In addition, a lithium ion battery is also needed to be provided.
The invention provides a lithium metal negative electrode which comprises a substrate and a surface layer formed on the substrate, wherein the substrate and the surface layer are both made of lithium metal or lithium alloy, a plurality of holes are formed in the surface layer, and the holes are mutually communicated to form a three-dimensional network structure.
The invention also provides a preparation method of the lithium metal negative electrode, which comprises the following steps:
preparing an oxidizing solution in an inert atmosphere;
providing a reaction substrate, wherein the material of the reaction substrate is lithium metal or lithium alloy; and
and contacting the reaction substrate and the oxidizing solution in the inert atmosphere, so that a part of the reaction substrate positioned on the surface is subjected to cavitation reaction in the oxidizing solution to form a surface layer, and the other part of the unreacted reaction substrate forms a base, thereby obtaining the lithium metal negative electrode.
The invention also provides a lithium ion battery comprising the lithium metal cathode.
The surface layer of the lithium metal negative electrode provided by the invention is lithium metal, so that the lithium metal negative electrode has high lithium affinity, and the lithium dissolution and deposition processes have extremely low overpotential; and the surface layer is provided with a plurality of holes which are communicated with each other to form a three-dimensional network structure, and the three-dimensional network structure is favorable for reducing the local current density and can effectively inhibit the formation of lithium dendrites.
Drawings
Fig. 1 is a schematic structural diagram of a lithium metal negative electrode according to a preferred embodiment of the present invention.
Fig. 2 is a scanning tunneling microscope image of a lithium metal negative electrode prepared in example 1 of the present invention.
Fig. 3 is a flow chart of a method of manufacturing a lithium metal negative electrode in a preferred embodiment of the invention.
Fig. 4 is a scanning tunneling microscope image of a lithium metal negative electrode prepared in example 1 of the present invention after electrochemical deposition.
Fig. 5 is a scanning tunneling microscope image of a lithium metal negative electrode prepared in comparative example 1 of the present invention after electrochemical deposition.
Fig. 6 is a potential-time diagram of a constant current dissolution deposition test after lithium metal cathodes prepared in example 1 of the present invention and comparative examples 1-2 were assembled into L i-L i symmetric cells, respectively.
Description of the main elements
Lithium metal negative electrode 100
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The preferred embodiment of the present invention provides a lithium metal negative electrode 100, which comprises a substrate 10 and a surface layer 20 formed on the substrate 10.
The substrate 10 is made of lithium metal or lithium alloy. In the present embodiment, the substrate 10 is a lithium metal sheet.
Referring to fig. 1 and 2, the material of the surface layer 20 is lithium metal or lithium alloy. The surface layer 20 is provided with a plurality of cavities 21, and the plurality of cavities 21 are communicated with each other to form a three-dimensional network structure. Wherein the diameter of the cavity 21 is 100nm-100 μm. Preferably, the diameter of the cavity 21 is 1 μm to 50 μm. The depth of the cavity 21 is 1 μm to 50 μm, and the specific surface area of the surface layer 20 is 20 to 90m2g-1。
Referring to fig. 3, a method for manufacturing the lithium metal negative electrode 100 according to a preferred embodiment of the present invention includes the following steps:
step S11, an oxidizing solution is prepared in an inert atmosphere.
Wherein the oxidizing solution comprises an oxidizing agent and an organic solvent. Wherein the oxidizing agent has an oxidizing effect on lithium metal; the organic solvent has good solubility to the oxidant, is stable to the lithium metal, and does not undergo a side reaction with the lithium metal. The oxidizing solution is formulated in an inert atmosphere to prevent reduction of the oxidizing agent.
In the embodiment, the oxidant comprises at least one of elementary iodine, elementary bromine and elementary chlorine, and the concentration of the oxidant is 1-50mg m L-1Preferably, the concentration of the oxidizing agent is 10-30mg m L-1. The organic solvent comprises at least one of tetrahydrofuran, carbon disulfide, N-methyl pyrrolidone, ethylene glycol methyl ether and ethylene glycol dimethyl ether. Preferably, the organic solvent is tetrahydrofuran.
In this embodiment, the inert atmosphere is argon. Wherein the mole fractions of oxygen and water vapor are less than 5ppm and less than 1ppm, respectively, in the inert atmosphere.
Step S12, providing a reaction substrate, wherein the reaction substrate is made of lithium metal or lithium alloy.
Step S13, contacting the reaction substrate with the oxidizing solution in the inert atmosphere, so that a portion of the reaction substrate on the surface is subjected to a cavitation reaction in the oxidizing solution to form a surface layer 20, and another portion of the reaction substrate which is not reacted forms a base 10, thereby obtaining the lithium metal negative electrode 100.
Specifically, the cavitation reaction includes charging the inert gas into the oxidizing agent to generate oxidizing bubbles, and etching a portion of the surface of the reaction substrate to form the surface layer 20. The surface layer 20 is provided with a plurality of cavities 21, and the cavities 21 are communicated with each other to form a three-dimensional network structure.
Wherein the bubble generation method comprises an ultrasonic treatment method, a high-speed stirring method and a gas filling method. Namely, the cavitation reaction comprises an ultrasonic treatment method, a high-speed stirring method and a gas filling method.
The ultrasonic treatment method is to seal the reaction substrate and the oxidizing solution in the inert atmosphere into a glass bottle, and then the glass bottle is transferred to the air for ultrasonic treatment. Wherein the ultrasonic frequency is 15-40 kHZ. Preferably, the ultrasound frequency is 20-35 kHZ. The ultrasonic time is 50-1200 s. Preferably, the sonication time is 100-. The ultrasonic temperature is 10-50 ℃. Preferably, the sonication temperature is 20-40 ℃.
The high-speed stirring method is to seal the reaction substrate, the oxidizing solution and the magnetons in the inert atmosphere into a glass bottle, and place the glass bottle on a magnetic stirrer for high-speed stirring. Wherein the stirring speed is 1000-. Preferably, the stirring speed is 2000-.
The gas filling method comprises the steps of putting the reaction substrate and the oxidizing solution into a glass bottle in the inert atmosphere, and filling the inert atmosphere into the glass bottle, wherein the inert atmosphere can be argon, and the flow rate of filling the inert atmosphere is 20-60L min-1Preferably, the inert atmosphere is charged at a flow rate of 40 to 50L min-1。
After the cavitation reaction, the lithium metal negative electrode 100 needs to be taken out in a protective atmosphere, and an oxide on the surface of the lithium metal negative electrode 100 needs to be cleaned by a cleaning agent and dried in the protective atmosphere. Wherein the protective atmosphere may be argon. In this embodiment, the cleaning agent includes at least one of tetrahydrofuran, ethylene glycol monomethyl ether, and n-hexane.
The present invention will be specifically described below by way of examples and comparative examples.
Example 1
First, 5m L with a concentration of 15mg m L was prepared in an argon protective glove box-1Iodine in tetrahydrofuran and stored in glass bottles. Wherein the mole fractions of oxygen and water vapor are less than 5ppm and less than 1ppm, respectively, in the argon protective atmosphere.
And secondly, soaking the lithium metal sheet in the iodine tetrahydrofuran solution, and sealing the glass bottle by using a sealing film.
And thirdly, transferring the packaged glass bottle into the air, and placing the glass bottle in ultrasonic equipment for ultrasonic treatment, wherein the ultrasonic frequency is set to be 20kHZ, the ultrasonic temperature is set to be 30 ℃, and the ultrasonic time is set to be 300 s.
And fourthly, transferring the glass bottle into the argon protective glove box, taking out the lithium metal sheet after ultrasonic treatment, and cleaning the treated lithium metal sheet by using a tetrahydrofuran cleaning agent to obtain the lithium metal cathode.
Example 2
This example differs from example 1 in that the concentration of iodine in the first step is 30mgm L-1。
Example 3
This example differs from example 1 in that the concentration of iodine in the first step is 5mgm L-1(ii) a The sonication time in the third step was 500 s.
Example 4
This example differs from example 1 in that: the sonication temperature in the third step was 20 ℃.
Example 5
This example differs from example 1 in that: in the first step, a solution of iodine in ethylene glycol monomethyl ether is prepared.
Example 6
This example differs from example 1 in that: in the third step a magnetic stirrer was added to the glass bottle, which was placed on a magnetic stirrer, setting the stirring speed at 1500rpm and the stirring time at 500 s.
Example 7
This example differs from example 6 in that: in the third step, the stirring rate was set at 4000rpm and the stirring time was set at 300 s.
Example 8
This example is different from example 1 in that the glass bottle was filled with argon gas in the third step and the flow rate of the argon gas was set to 45L min-1The argon gas was introduced for 500 seconds.
Example 9
The examples are given inExample 8 was repeated except that the flow rate of argon gas fed in the third step was set to 65L min-1The argon gas was introduced for 300 seconds.
Comparative example 1
An untreated lithium metal sheet was used as the lithium metal negative electrode.
Comparative example 2
In the first step, a 5m solution of L tetrahydrofuran was taken in an argon-protected glove box and stored in a glass bottle, wherein the mole fractions of oxygen and water vapor were below 5ppm and 1ppm, respectively, in the argon-protected atmosphere.
The second step to the fourth step are the same as the second step to the fourth step in example 1, specifically, refer to example 1.
Comparative example 3
This comparative example differs from comparative example 2 in that in the first step a concentration of 5m L of 15mg m L was made in an argon-protected glove box-1A tetrahydrofuran solution of iodine and storing the tetrahydrofuran solution in a glass bottle; and in the third step, the lithium metal sheet is taken out after being soaked in the iodine tetrahydrofuran solution for 300 s.
Comparative example 4
This comparative example differs from comparative example 2 in that in a first step 75mg of iodine were added to 5m L n-hexane stored in a glass bottle, which only precipitated as solid particles at the bottom, since iodine was not soluble in n-hexane.
The lithium metal negative electrodes obtained in examples 1 to 9 and the lithium metal negative electrode obtained in the comparative example were subjected to a scanning electron microscope test, respectively. Specific test results are shown in table 1, and referring to fig. 2 (fig. 2 is an electron microscope image of example 1, and electron microscope images of examples 2 to 9 are not shown), a plurality of cavities are formed on the surface of each of the lithium metal cathodes obtained in examples 1 to 9, and the cavities are communicated with each other to form a three-dimensional network structure. The surface of the lithium metal negative electrode in comparative example 1 was a gully-shaped surface. The surface of the lithium metal negative electrode obtained in comparative example 2 still maintained the original gully-shaped surface of the lithium metal sheet, and the three-dimensional network structure was not generated. The surfaces of the lithium metal negative electrodes obtained in comparative examples 3 to 4 also did not develop the three-dimensional network structure.
The lithium metal negative electrodes obtained in examples 1 to 9 and the lithium metal negative electrode obtained in comparative example were each charged at 1mA cm-2The current density of the anode is subjected to electrochemical deposition for 2 hours, and the current density is respectively subjected to scanning electron microscope test. Referring to fig. 4 and 5 (fig. 4 is an electron microscope image of example 1, fig. 5 is an electron microscope image of comparative example 1, and electron microscope images of other examples and comparative examples are not shown), it is shown that no significant dendrite appears on the surface of the lithium metal negative electrodes prepared in examples 1-9, but significant dendrite appears on the surface of the lithium metal negative electrodes prepared in comparative examples 1-4.
Then, L i-L i symmetrical batteries were assembled by using the lithium metal negative electrodes obtained in examples 1-9 and the lithium metal negative electrode obtained in comparative example, respectively, at 1mAcm-2Current density of 1mAh cm-2The deposition depth of (a) was tested for solvent deposition. The test conditions and the test results are shown in table 1, and referring to fig. 6, a short circuit phenomenon in which the overpotential sharply increases was observed after 50 hours of the cycle in comparative example 1; a short circuit phenomenon in which the overpotential sharply increases was observed after 100 hours of cycles in both comparative example 2 and comparative example 4.
TABLE 1 scanning Electron microscope test results, solvent deposition test conditions and test results for inventive examples 1-9 and comparative examples
Example 1 compared to comparative example 1 illustrates that: when lithium metal without a three-dimensional structure on the surface is directly used as a negative electrode to perform electrochemical reaction, the overpotential is high, the potential is unstable, the cycle life is short, and dendritic crystals are easily formed. The examples are illustrated in comparison with comparative example 2: without using an oxidizing agent, only ultrasonic treatment is performed, and a surface layer having the three-dimensional network structure cannot be formed on the reaction substrate, so that a low overpotential cannot be obtained. Example 1 compared to comparative example 3 illustrates: the use of only an oxidizing agent without performing a cavitation reaction can only change the morphology of the reaction substrate, and cannot form a surface layer having the three-dimensional network structure on the reaction substrate. The comparison of the examples with comparative example 4 shows that: only when the oxidizing agent is dissolved in the solution to form a uniform oxidizing atmosphere, bubbles having oxidizing properties are formed, thereby forming a surface layer having the three-dimensional network structure on the reaction substrate. Comparison of the examples with comparative examples 1-4 illustrates: the overpotential of the lithium metal negative electrode can be effectively reduced only by forming the surface layer with the three-dimensional network structure on the reaction substrate, and the service life of the lithium metal negative electrode is prolonged.
The invention has the following advantages:
(1) the surface layer 20 of the lithium metal negative electrode 100 is provided with a plurality of holes 21, the holes 21 are communicated with each other to form a three-dimensional network structure, and the three-dimensional network structure is beneficial to reducing local current density and can effectively inhibit the formation of lithium dendrites.
(2) Compared with the conventional three-dimensional current collector, the three-dimensional network structure is constructed in situ through a cavitation erosion effect, other material frameworks are not required to be introduced, the quality of the electrode can be improved due to the introduction of other framework structures, and therefore the same ultrahigh theoretical specific capacity as the lithium metal negative electrode 100 can be obtained.
(3) In the present invention, the surface layer 20 is made of lithium metal, and has a very high lithium affinity, so that the lithium dissolution and deposition processes have a very low overpotential.
(4) L i, the oxidizing agent used in the present invention is effective in removing the inertness of the reaction substrate surface2O and L i2CO3The reaction activity of the reaction substrate is improved, and a uniform and stable solid electrolyte interface is formed in the cyclic charge-discharge process.
(5) The invention uses ultrasonic method to carry out 'cavitation' reaction, and has simple operation and low cost.
(6) The lithium metal negative electrode 100 prepared in the present invention can be directly used for the assembly of a lithium metal battery having a low negative overpotential (1mA cm)-2Less than or equal to 30mV), and long cycle stability (which can be cycled for more than 600 hours).
Although the embodiments of the present invention have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the embodiments of the present invention.
Claims (10)
1. The lithium metal negative electrode is characterized by comprising a substrate and a surface layer formed on the substrate, wherein the substrate and the surface layer are both made of lithium metal or lithium alloy, a plurality of holes are formed in the surface layer, and the holes are mutually communicated to form a three-dimensional network structure.
2. The lithium metal negative electrode of claim 1, wherein the cavities have a diameter of 100nm to 100 μm and a depth of 1 μm to 50 μm.
3. The lithium metal negative electrode of claim 1, wherein the surface layer has a specific surface area of 20 to 90m2g-1。
4. A method of making a lithium metal anode according to any of claims 1 to 3, comprising the steps of:
preparing an oxidizing solution in an inert atmosphere;
providing a reaction substrate, wherein the material of the reaction substrate is lithium metal or lithium alloy; and
and contacting the reaction substrate and the oxidizing solution in the inert atmosphere, so that a part of the reaction substrate positioned on the surface is subjected to cavitation reaction in the oxidizing solution to form a surface layer, and the other part of the unreacted reaction substrate forms a base, thereby obtaining the lithium metal negative electrode.
5. The method of making a lithium metal anode of claim 4, wherein the oxidizing solution comprises an oxidizing agent and an organic solvent.
6. The method of claim 5, wherein the oxidant comprises at least one of elemental iodine, elemental bromine, and elemental chlorine, and the concentration of the oxidant is 1-50mg m L-1。
7. The method of claim 5, wherein the organic solvent comprises at least one of tetrahydrofuran, carbon disulfide, N-methylpyrrolidone, ethylene glycol methyl ether, and ethylene glycol dimethyl ether.
8. The method of making a lithium metal anode of claim 4, wherein contacting the reaction substrate and the oxidizing solution in the inert atmosphere comprises:
sealing the reaction substrate and the oxidizing solution into a glass bottle in the inert atmosphere, and transferring the glass bottle to the air for ultrasonic treatment; or
Sealing the reaction substrate, the oxidizing solution and the magnetons in the inert atmosphere into a glass bottle, and placing the glass bottle on a magnetic stirrer for stirring; or
And (3) putting the reaction substrate and the oxidizing solution into a glass bottle in the inert atmosphere, and filling the glass bottle with the inert atmosphere.
9. The method of making a lithium metal anode of claim 4, further comprising, during the cavitation reaction:
and cleaning the oxide on the surface of the lithium metal negative electrode in a protective atmosphere.
10. A lithium ion battery comprising the lithium metal negative electrode according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010228963.2A CN111403687A (en) | 2020-03-27 | 2020-03-27 | Lithium metal cathode, preparation method and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010228963.2A CN111403687A (en) | 2020-03-27 | 2020-03-27 | Lithium metal cathode, preparation method and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111403687A true CN111403687A (en) | 2020-07-10 |
Family
ID=71413674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010228963.2A Pending CN111403687A (en) | 2020-03-27 | 2020-03-27 | Lithium metal cathode, preparation method and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111403687A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022259871A1 (en) * | 2021-06-08 | 2022-12-15 | 国立大学法人東海国立大学機構 | Negative electrode for lithium-ion secondary battery, manufacturing method and manufacturing device therefor, and lithium-ion secondary battery |
| KR102673555B1 (en) * | 2021-05-27 | 2024-06-10 | 서울대학교산학협력단 | Manufacturing method for metal anode using bromination reagent, the anode and secondary cell including the anode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784636A (en) * | 2016-12-29 | 2017-05-31 | 中国电子科技集团公司第十八研究所 | Method for treating surface of metal lithium by using iodine solution and application of method in solid-state battery |
| CN108796504A (en) * | 2018-01-19 | 2018-11-13 | 苏州大学 | A kind of preparation method of 3-dimensional metal cathode |
| CN108832116A (en) * | 2018-06-20 | 2018-11-16 | 成都爱敏特新能源技术有限公司 | A kind of sheet metal lithium powder and preparation method thereof |
| CN109585786A (en) * | 2018-12-04 | 2019-04-05 | 安徽盟维新能源科技有限公司 | A kind of guard method and its application of lithium an- ode |
| CN109585947A (en) * | 2018-12-04 | 2019-04-05 | 安徽盟维新能源科技有限公司 | A kind of lithium an- ode double protection method and application |
| CN110444735A (en) * | 2019-07-17 | 2019-11-12 | 湖南立方新能源科技有限责任公司 | A kind of surface modifying method and lithium metal battery of lithium metal battery cathode |
-
2020
- 2020-03-27 CN CN202010228963.2A patent/CN111403687A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784636A (en) * | 2016-12-29 | 2017-05-31 | 中国电子科技集团公司第十八研究所 | Method for treating surface of metal lithium by using iodine solution and application of method in solid-state battery |
| CN108796504A (en) * | 2018-01-19 | 2018-11-13 | 苏州大学 | A kind of preparation method of 3-dimensional metal cathode |
| CN108832116A (en) * | 2018-06-20 | 2018-11-16 | 成都爱敏特新能源技术有限公司 | A kind of sheet metal lithium powder and preparation method thereof |
| CN109585786A (en) * | 2018-12-04 | 2019-04-05 | 安徽盟维新能源科技有限公司 | A kind of guard method and its application of lithium an- ode |
| CN109585947A (en) * | 2018-12-04 | 2019-04-05 | 安徽盟维新能源科技有限公司 | A kind of lithium an- ode double protection method and application |
| CN110444735A (en) * | 2019-07-17 | 2019-11-12 | 湖南立方新能源科技有限责任公司 | A kind of surface modifying method and lithium metal battery of lithium metal battery cathode |
Non-Patent Citations (1)
| Title |
|---|
| 柳伟等: "金属材料的空蚀研究进展", 《中国腐蚀与防护学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102673555B1 (en) * | 2021-05-27 | 2024-06-10 | 서울대학교산학협력단 | Manufacturing method for metal anode using bromination reagent, the anode and secondary cell including the anode |
| WO2022259871A1 (en) * | 2021-06-08 | 2022-12-15 | 国立大学法人東海国立大学機構 | Negative electrode for lithium-ion secondary battery, manufacturing method and manufacturing device therefor, and lithium-ion secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109004276A (en) | A kind of cathode of lithium protective film, preparation method and lithium metal secondary cell | |
| CN111354939B (en) | Porous silicon composite material and preparation method and application thereof | |
| CN109216681B (en) | Based on TiO2Lithium metal cathode material of nanotube array/titanium foam and preparation method thereof | |
| CN107394176B (en) | Silicon-carbon composite material, preparation method and application thereof, and lithium ion battery cathode material | |
| CN108493485A (en) | A kind of preparation method of high power capacity high safety solid state lithium battery | |
| CN111952567A (en) | Organic lithium-philic composite cathode taking three-dimensional conductive carbon material as substrate and preparation method thereof | |
| CN109326798B (en) | Preparation method and application of metal lithium negative electrode protection layer | |
| CN111403687A (en) | Lithium metal cathode, preparation method and lithium ion battery | |
| WO2023197806A1 (en) | Porous polymer coating copper electrode and preparation method therefor and application thereof | |
| Lu et al. | Dual-regulation of ions/electrons in a 3D Cu–Cu x O host to guide uniform lithium growth for high-performance lithium metal anodes | |
| CN111193031A (en) | Lithium metal battery cathode and modification method thereof | |
| CN112768697A (en) | Composite lithium metal negative current collector and preparation method and application thereof | |
| CN114284475B (en) | Preparation method of three-dimensional structured composite lithium metal anode and product thereof | |
| CN113964289A (en) | Surface organic phosphoric acid etched composite zinc-philic passive film modified zinc metal cathode and preparation method and application thereof | |
| CN115732643A (en) | Halogenated solid electrolyte interface layer composite electrode material based on solid source plasma and preparation method and application thereof | |
| CN114792775A (en) | Polymer coating modified zinc cathode and preparation method and application thereof | |
| CN114361402A (en) | MXene-based modified layer dendrite-free lithium metal negative electrode, preparation method thereof and lithium metal battery | |
| KR20190108316A (en) | Method for a porous electrode current collector for lithium metal battery using hydrogen bubble as a template and electrode current collector manufactured thereby | |
| CN112421115A (en) | Lithium metal-based battery with copper selenide in-situ coated foam copper as lithium metal carrier and preparation method thereof | |
| CN112072076A (en) | Modification method for surface of negative electrode of lithium metal battery | |
| CN113013400A (en) | Modified lithium metal negative electrode, preparation method and battery thereof | |
| KR102398953B1 (en) | Zinc ion secondary battery in which zinc dendrite formation is suppressed, electrochemically derived zincophilic 3d graphene carbon sheet, and method for manufacturing the same | |
| CN115732783A (en) | Composite metal lithium cathode with artificial solid electrolyte interface layer and preparation method and application thereof | |
| KR102085499B1 (en) | Method for a porous electrode current collector for lithium metal battery using hydrogen bubble as a template and electrode current collector manufactured thereby | |
| CN111640929B (en) | Preparation method of organic-inorganic ordered SEI layer modified lithium metal and application of organic-inorganic ordered SEI layer modified lithium metal in electrochemical field |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200710 |
|
| RJ01 | Rejection of invention patent application after publication |