CN113130854A - Preparation method of dendrite-free lithium metal-graphene paper composite negative electrode - Google Patents
Preparation method of dendrite-free lithium metal-graphene paper composite negative electrode Download PDFInfo
- Publication number
- CN113130854A CN113130854A CN202110365661.4A CN202110365661A CN113130854A CN 113130854 A CN113130854 A CN 113130854A CN 202110365661 A CN202110365661 A CN 202110365661A CN 113130854 A CN113130854 A CN 113130854A
- Authority
- CN
- China
- Prior art keywords
- graphene paper
- negative electrode
- dendrite
- lithium metal
- graphene
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000004070 electrodeposition Methods 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003828 vacuum filtration Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of 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
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a dendrite-free lithium metal-graphene paper composite negative electrode. The lithium metal and the graphene paper framework are compounded in an electrochemical deposition mode, and deposited lithium is uniformly dispersed in the graphene paper framework in a particle form. Lithium deposited in the graphene paper framework is in a dendrite-free form, and the form is still maintained in the subsequent battery circulation process, so that the failure of the battery caused by lithium dendrite is eliminated; the graphene paper framework is a loose and porous three-dimensional structure formed by graphene, has excellent electronic and ionic conductivity and is suitable for high-power use environments; the prepared composite cathode has good flexibility and is suitable for flexible devices.
Description
Technical Field
The invention relates to the technical field of phase modification of a lithium metal negative electrode, in particular to a method for inhibiting growth of lithium dendrites of a lithium metal negative electrode.
Background
With the continuous progress of society, various portable electronic products are becoming an essential part of human daily life. Lithium ion batteries are widely used in various fields such as camcorders, mobile phones, notebook computers, electric vehicles, and the like due to their characteristics of high operating voltage, good cycle performance, high energy density, high power density, and the like. However, with the demand increasing, the traditional lithium ion battery can not meet the requirement, and the development of an electrode material with high energy density and long service life is urgently needed to meet the requirement of a new high-end energy storage device.
The lithium metal negative electrode is known as a "holy-cup" electrode with its extremely high theoretical capacity (3860mAh/g) and most negative potential (-3.040Vvs standard hydrogen electrode), and is of great interest to researchers.
However, these lithium metal batteries have serious dendrite growth problems and are difficult to stably cycle. Lithium dendrite growth can lead to short circuits in the battery and can lead to thermal runaway, creating a potential risk of fire explosion, and lithium dendrites can also form "dead lithium" causing irreversible loss of battery capacity. These safety problems have resulted in the failure of lithium metal secondary batteries to be commercially used. In recent years, researchers have proposed various solutions to the use of lithium metal as a commercial negative electrode material, but none of them can completely solve the problem of lithium dendrite growth fundamentally, and therefore, the development of effective technology for suppressing lithium dendrite is the key to the development of high-specific-capacity lithium metal batteries.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for inhibiting the growth of lithium dendrite, and the method provided by the invention constructs a three-dimensional structure framework for lithium metal, can obviously inhibit the growth of the dendrite and improves the stability of the lithium metal in the circulation process.
The invention provides a method for preparing a graphene paper skeleton with a three-dimensional structure, which inhibits the growth of lithium dendrites by constructing a lithium metal-graphene paper skeleton composite negative electrode, and comprises the following steps:
(1) preparing a certain amount of graphene aqueous solution, performing ultrasonic dispersion, removing water in a vacuum filtration mode, adding a proper amount of absolute ethyl alcohol in the vacuum filtration process, heating and drying after removing the water, and separating the graphene stacking polymer from the filter membrane to obtain the loose and porous graphene paper framework.
(2) A graphene paper framework is used as a positive electrode, a pure lithium sheet is used as a negative electrode, a button cell type electrodeposition device is assembled in the sequence of a negative electrode shell, a lithium sheet, a diaphragm, graphene paper, a spring sheet, a stainless steel gasket and a positive electrode shell, and lithium metal and the graphene paper framework are compounded in an electrochemical deposition mode.
Further, in the step (1), the concentration of the graphene aqueous solution used is 0.1mg/mL, and the volume of the graphene solution used is 300 mL.
In the step (1), the liquid temperature of the ultrasonic treatment is 25 ℃, and the ultrasonic treatment time is 20 min.
In the step (1), the filter membrane used in vacuum filtration is an anodic alumina template (AAO), the diameter is 47mm, and the aperture is 200 nm.
In step (1), before the suction filtration starts, 50mL of absolute ethanol is added to the suction filtration vessel, and when the amount of the solution remaining in the vessel is 4/5, 3/5, 2/5, 1/5, 5mL of absolute ethanol is added, respectively.
In the step (1), the heating and drying temperature is 60 ℃ and the time is 4 h.
In the step (2), the diameters of the lithium sheet, the diaphragm and the graphene paper are the same and are all 12 mm.
In step (2), the lithium sheet has a thickness of 500. mu.m.
In the step (2), a glass fiber membrane is used as the separator.
In the step (2), the electrolyte is injected into the electrodeposition equipment to be 1mol/L LiPF 6100. mu.L of the EC/DMC (1:1) solution of (3).
In the step (2), the electrodeposition process is a constant current discharge process with a current density of 1mA/cm2The deposition time was 4 h.
By means of the scheme, the invention has the following advantages:
the method can obviously inhibit the generation of lithium dendrites, the graphene paper serving as a lithium framework has a three-dimensional structure, the local current density can be reduced, sufficient lithium nucleation points are provided, the growth of the lithium dendrites is effectively inhibited, and in addition, the loose and porous structure can ensure the rapid transmission of ions and electrons and enhance the rate capability of the lithium dendrites. The graphene paper framework has excellent strength and flexibility, can accommodate the volume change of lithium, resists electrode deformation, and is suitable for flexible devices. The characteristics enable the graphene paper to avoid capacity loss caused by dendritic crystal formation when the graphene paper is compounded with lithium metal and used as a battery cathode, ensure good cycle performance, greatly improve the stability of the graphene paper in the cycle process and obviously prolong the cycle life of the battery. The method has the characteristics of simple preparation process, high efficiency, stable effect, environmental friendliness and high safety.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood and to be implemented in accordance with the content of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is a schematic diagram of a process for preparing a graphene paper skeleton with a three-dimensional structure according to an embodiment;
FIG. 2 is a topographical view of a prepared graphene paper skeleton;
FIG. 3 is a schematic diagram of an electrodeposition process for compounding lithium and graphene paper;
FIG. 4 is a topography of a lithium-graphene paper composite pole piece;
FIG. 5 shows that the ratio of the lithium-graphene paper composite pole piece to the pure lithium symmetrical battery is 1mA/cm2Current density of (a);
fig. 6 is a test chart of cycle performance of a button cell assembled by a lithium-graphene paper composite pole piece, a pure lithium symmetric cell and a Lithium Cobaltate (LCO) positive electrode material.
Detailed Description
In order to more clearly illustrate the embodiments or technical solutions in the prior art, the technical solutions in the embodiments of the present invention will be described in detail 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. The following examples are intended to illustrate the invention, but are not intended to limit the scope thereof;
the invention aims to provide a method for protecting lithium metal and inhibiting the formation of lithium dendrites, thereby obviously improving the stability of a lithium metal battery in the working cycle process, and improving the safety and the service life of the battery.
Example one
The invention provides a method for preparing a three-dimensional graphene paper skeleton, and the growth of lithium dendrites is inhibited by constructing a lithium metal-graphene paper skeleton composite negative electrode, fig. 1 is a schematic diagram of a preparation process of the three-dimensional graphene paper skeleton, and the preparation process is as shown in fig. 1: preparing 300mL of 0.1mg/mL graphene aqueous solution, ultrasonically dispersing at 20 ℃ for 20min, and removing water in a vacuum filtration mode, wherein the used filter membrane is an anodic alumina template (AAO), the diameter of the filter membrane is 47mm, and the pore diameter of the filter membrane is 200 nm. In the vacuum filtration process, 50mL of absolute ethanol is added to the filtration vessel before the filtration is started, and 5mL of absolute ethanol is added when the amount of the solution remaining in the vessel is 4/5, 3/5, 2/5 and 1/5, respectively. And (3) after the moisture is removed, heating at 60 ℃ for 4h for drying, and separating the graphene stacking polymer from the filter membrane to obtain the loose and porous graphene paper framework.
Fig. 3 is a schematic diagram of a process of compounding lithium and graphene paper by an electrodeposition method, and the implementation flow is as follows: a graphene paper framework is used as a positive electrode, a pure lithium sheet is used as a negative electrode, a button cell type electrodeposition device is assembled in the sequence of a negative electrode shell, a lithium sheet, a diaphragm, graphene paper, a spring piece, a stainless steel gasket and a positive electrode shell, the diameters of the lithium sheet, the diaphragm and the graphene paper are the same and are all 12mm, the lithium sheet with the thickness of 500 mu m is selected, and a glass fiber membrane is used as the diaphragm. Before the encapsulation of the electrodeposition apparatus, 100. mu.L of 1mol/L EC/DMC (1:1) solution of LiPF6 was injected. Compounding lithium metal and a graphene paper framework in an electrochemical deposition mode, wherein the electrodeposition process is a constant-current discharge process, the current density is 1mA/cm2, and the deposition time is 4 h.
Example two
Preparing a lithium metal-graphene paper composite pole piece according to the experimental method, assembling a symmetrical battery by using the composite lithium pole piece, and selecting LiPF6A solute is dissolved in EC and DMC (volume ratio is 1:1) to be used as an electrolyte (1mol/L), and a glass fiber membrane is used as a diaphragm to be used as an experimental group. Assembled with pure lithium sheetsThe symmetric cells served as control. The cycling stability of both groups of cells was tested under the following test conditions: at 1mA/cm2Charging and discharging the current density of (1). The test results are shown in FIG. 5. The overpotential of the symmetrical battery of the unprotected control group fluctuates sharply in 0-15 circles, and then in 15-60 circles, the cycle is stable, the overpotential value is kept at about 110mv, and then the overpotential rapidly increases over 400 mv. The circulation process keeps larger overpotential, which indicates that serious side reaction occurs in the symmetrical battery and generates side reaction products with larger impedance; the stable circulation of the experimental group symmetrical battery exceeds 600 circles, the average overpotential in the circulation process is about 30mv, and the result proves that the lithium metal-graphene paper composite pole piece without dendrites can effectively inhibit the fluctuation of the battery performance caused by side reactions derived from dendrites and maintain the long-time stable circulation.
EXAMPLE III
And (3) selecting an LCO material as a positive electrode, preparing a lithium metal-graphene paper composite pole piece according to the experimental method, and using the composite lithium pole piece as a negative electrode of the battery. LiPF is selected6In order to dissolve solute in EC and DMC (volume ratio is 1:1) as electrolyte (1mol/L), glass fiber membrane is used as diaphragm to assemble half-cell as experimental group. And a pure lithium plate is used as a negative electrode, and the positive electrode is still made of LCO material, so that another half cell is assembled to serve as a control group. The performance of both groups of cells was tested under the following test conditions: the first five cycles of charging and discharging at a current multiplying factor of 0.2C, and then charging and discharging at a current multiplying factor of 1C, wherein the charging and discharging window is 3.0-4.2V, and the test result is shown in figure 6. The composite lithium negative electrode battery can maintain stable circulation for a long time, the capacity retention rate can still reach 82.1% after 400 circles, and the coulombic efficiency is always stabilized at about 100%. In comparison, a pure lithium sheet cathode battery can maintain relatively stable circulation in the initial stage, however, after 120 circles, the battery capacity has avalanche type downslide, and within 45 circles, the capacity has dropped to about 0, and correspondingly, the coulombic efficiency has obvious fluctuation after 120 circles, and the downslide of the capacity is due to the formation of lithium dendrites in the circulation process.
The present specification uses specific examples to illustrate the embodiments of the present invention, and the above description of the embodiments is only used to help understanding the method and the core idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. A preparation method of a dendrite-free lithium metal-graphene paper composite negative electrode is characterized by comprising the following steps:
(1) preparing a certain amount of graphene aqueous solution, performing ultrasonic dispersion, removing water in a vacuum filtration mode, adding a proper amount of absolute ethyl alcohol in the vacuum filtration process, heating and drying after removing water, and separating a graphene stacking polymer from a filter membrane to obtain a loose and porous graphene paper framework;
(2) a graphene paper framework is used as a positive electrode, a pure lithium sheet is used as a negative electrode, a button cell type electrodeposition device is assembled in the sequence of a negative electrode shell, a lithium sheet, a diaphragm, graphene paper, a spring sheet, a stainless steel gasket and a positive electrode shell, and lithium metal and the graphene paper framework are compounded in an electrochemical deposition mode.
2. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (1), the concentration of the used graphene aqueous solution is 0.05-0.2mg/mL, and the volume of the used graphene solution is 100-; in the step (1), the liquid temperature of the ultrasonic treatment is 10-30 ℃, and the ultrasonic treatment time is 10-40 min.
3. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (1), the filter membrane used in vacuum filtration is an anodic alumina template (AAO), the diameter is 47-55mm, and the aperture is 50-200 nm.
4. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (1), before the suction filtration is started, 20-100mL of absolute ethyl alcohol is added into a suction filtration container, and when the amount of the solution remained in the container is 4/5, 3/5, 2/5 and 1/5, 2-5mL of absolute ethyl alcohol is respectively added.
5. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (1), the heating and drying temperature is 40-80 ℃ and the time is 1-4 h.
6. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (2), the diameters of the lithium sheet, the diaphragm and the graphene paper are the same and are all 12-16 mm.
7. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (2), the thickness of the lithium sheet is 50 to 500 μm.
8. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (2), a glass fiber membrane is used as the separator.
9. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (2), the electrolyte is injected into the electrodeposition equipment to be 1mol/L LiPF650-100. mu.L of the EC/DMC (1:1) solution of (2).
10. The method for preparing a dendrite-free lithium metal-graphene paper composite negative electrode according to claim 1, wherein the method comprises the following steps: in the step (2), the electrodeposition process is a constant current discharge process, and the current density is 0.5-2mA/cm2The deposition time is 2-8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110365661.4A CN113130854A (en) | 2021-04-06 | 2021-04-06 | Preparation method of dendrite-free lithium metal-graphene paper composite negative electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110365661.4A CN113130854A (en) | 2021-04-06 | 2021-04-06 | Preparation method of dendrite-free lithium metal-graphene paper composite negative electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113130854A true CN113130854A (en) | 2021-07-16 |
Family
ID=76774890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110365661.4A Pending CN113130854A (en) | 2021-04-06 | 2021-04-06 | Preparation method of dendrite-free lithium metal-graphene paper composite negative electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113130854A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117023569A (en) * | 2023-08-17 | 2023-11-10 | 小米汽车科技有限公司 | Graphene electrothermal film and preparation method thereof, negative electrode, lithium metal battery and dendrite removing method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784635A (en) * | 2017-01-13 | 2017-05-31 | 北京科技大学 | A kind of solid state battery preparation method for being combined cathode of lithium |
| CN107221709A (en) * | 2017-06-09 | 2017-09-29 | 清华大学 | The lithium metal battery preparation method that a kind of flexibility is filled soon |
| CN107910496A (en) * | 2017-10-09 | 2018-04-13 | 中南大学 | A kind of secondary cell lithium anode, preparation method and applications |
| CN109449376A (en) * | 2018-12-20 | 2019-03-08 | 国联汽车动力电池研究院有限责任公司 | A kind of compound metal lithium electrode and preparation method thereof |
| CN109841797A (en) * | 2018-11-21 | 2019-06-04 | 华南理工大学 | A kind of high-performance complex lithium metal negative electrode material and preparation method thereof based on graphene |
| CN111211292A (en) * | 2019-11-22 | 2020-05-29 | 中国科学院大连化学物理研究所 | Three-dimensional graphene composite lithium alloy cathode, preparation method thereof and application of three-dimensional graphene composite lithium alloy cathode in lithium ion battery |
| CN111224069A (en) * | 2020-01-17 | 2020-06-02 | 南京邮电大学 | Flexible self-supporting stainless steel mesh/graphene/lithium composite negative electrode and preparation method thereof |
-
2021
- 2021-04-06 CN CN202110365661.4A patent/CN113130854A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784635A (en) * | 2017-01-13 | 2017-05-31 | 北京科技大学 | A kind of solid state battery preparation method for being combined cathode of lithium |
| CN107221709A (en) * | 2017-06-09 | 2017-09-29 | 清华大学 | The lithium metal battery preparation method that a kind of flexibility is filled soon |
| CN107910496A (en) * | 2017-10-09 | 2018-04-13 | 中南大学 | A kind of secondary cell lithium anode, preparation method and applications |
| CN109841797A (en) * | 2018-11-21 | 2019-06-04 | 华南理工大学 | A kind of high-performance complex lithium metal negative electrode material and preparation method thereof based on graphene |
| CN109449376A (en) * | 2018-12-20 | 2019-03-08 | 国联汽车动力电池研究院有限责任公司 | A kind of compound metal lithium electrode and preparation method thereof |
| CN111211292A (en) * | 2019-11-22 | 2020-05-29 | 中国科学院大连化学物理研究所 | Three-dimensional graphene composite lithium alloy cathode, preparation method thereof and application of three-dimensional graphene composite lithium alloy cathode in lithium ion battery |
| CN111224069A (en) * | 2020-01-17 | 2020-06-02 | 南京邮电大学 | Flexible self-supporting stainless steel mesh/graphene/lithium composite negative electrode and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 曹天赐: "锂金属-石墨烯纸复合负极性能及其机理研究", 《中国优秀博硕学位论文全文数据库（硕士） 基础学科辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117023569A (en) * | 2023-08-17 | 2023-11-10 | 小米汽车科技有限公司 | Graphene electrothermal film and preparation method thereof, negative electrode, lithium metal battery and dendrite removing method thereof |
| CN117023569B (en) * | 2023-08-17 | 2024-05-07 | 小米汽车科技有限公司 | Graphene electrothermal film and preparation method thereof, negative electrode, lithium metal battery and dendrite removing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108172761B (en) | Composite negative electrode for lithium secondary battery, and preparation and application thereof | |
| JP4249607B2 (en) | Composite polymer electrolyte for lithium secondary battery containing single ion conductor and method for producing the same | |
| WO2011079482A1 (en) | Battery | |
| CN111463403A (en) | Negative electrode material modified by composite artificial solid electrolyte interface film and battery application thereof | |
| JP2002359005A (en) | Separator for wound lithium secondary battery containing gel polymer electrolyte and its manufacturing method | |
| CN109273704A (en) | A kind of lithium anode and preparation method thereof with high-ratio surface protective layer | |
| CN109546089B (en) | Silicon-based thin film composite pole piece, preparation method thereof and lithium ion battery | |
| CN110289448B (en) | Metal lithium cathode with artificially constructed SEI film and preparation method thereof | |
| CN103367791B (en) | A kind of new type lithium ion battery | |
| CN111073184B (en) | Gel electrolyte film for secondary battery, preparation and application thereof | |
| CN110911689A (en) | Current collector and preparation method thereof, electrode plate and secondary battery | |
| CN110444803A (en) | A kind of lithium ion battery structure of semisolid and preparation method thereof | |
| CN111403739A (en) | Nickel-cobalt-manganese acid lithium battery cell positive electrode active material, aluminum shell battery cell and manufacturing method thereof | |
| CN114203976A (en) | Mixed solution capable of improving stability of metal lithium cathode, preparation method and application | |
| CN111864180A (en) | Composite lithium metal cathode, preparation method thereof and lithium secondary battery | |
| CN113130854A (en) | Preparation method of dendrite-free lithium metal-graphene paper composite negative electrode | |
| CN116470003A (en) | Pre-lithiated negative electrode piece and lithium ion battery | |
| WO2024066087A1 (en) | Secondary battery and electrical apparatus | |
| CN115732783A (en) | Composite metal lithium cathode with artificial solid electrolyte interface layer and preparation method and application thereof | |
| CN109659475A (en) | A kind of preparation method of high-performance high-voltage lithium ion battery | |
| CN114927762A (en) | Fluorinated sulfonyl electrolyte, preparation method and application thereof, and lithium metal battery | |
| JP2006156228A (en) | Non-aqueous electrolyte secondary battery | |
| CN114512633A (en) | Negative plate and battery comprising same | |
| CN209747641U (en) | composite lithium metal negative electrode and lithium secondary battery | |
| CN108400374A (en) | A kind of high specific energy lithium ion battery |
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: 20210716 |
|
| RJ01 | Rejection of invention patent application after publication |