CN111193010B - Lithium battery composite material - Google Patents
Lithium battery composite material Download PDFInfo
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- CN111193010B CN111193010B CN202010016034.5A CN202010016034A CN111193010B CN 111193010 B CN111193010 B CN 111193010B CN 202010016034 A CN202010016034 A CN 202010016034A CN 111193010 B CN111193010 B CN 111193010B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a lithium battery composite material which comprises a solid electrolyte and a metal mixed melt coating which is used as a cathode and coated on the surface of the solid electrolyte, wherein the metal mixed melt coating is a mixed melt of metal lithium, metal zinc and lithium oxide. According to the lithium battery composite material, the metal lithium, the metal zinc and the lithium oxide form a mixed melt and then are coated on the surface of the solid electrolyte to form a coating, so that the specific surface area difference between the cathode material and the contact surface of the solid electrolyte is reduced, the lithium battery composite material has smaller impedance and conductivity, and the charging and discharging performance is better.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a lithium battery composite material.
Background
Lithium ion batteries are widely used as a source of numerous electronic products and power equipment. Since the liquid organic lithium ion battery is easily and violently burned when being collided or punctured, and personnel or property loss is caused, the all-solid lithium ion battery is an energy storage device with higher safety. But because the molten metal lithium and the solid electrolyte have huge specific surface energy, the metal lithium cannot spread in the solid electrolyte, so that the solid electrolyte and the metal lithium have huge ion transmission resistance which is as high as 2319 omega cm -2 And poor interface contact between the molten metal lithium and the solid electrolyte causes non-uniform ion transmission paths, so that local current is too large, growth of lithium dendrite is accelerated, and finally the battery is short-circuited. An inorganic-organic composite solid electrolyte is described in the invention patent application No. 201810210158.X, butAt present, the conductivity of an organic solid electrolyte is one to two orders of magnitude lower than that of an inorganic solid electrolyte, so that the conductivity of the electrolyte is lower than that of the inorganic solid electrolyte, and the mechanical strength of the solid electrolyte is reduced due to the addition of organic matters, the overall compactness is reduced, the solid electrolyte is easy to puncture by lithium dendrites, and the battery is easy to be short-circuited, so that serious accidents are caused.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a lithium battery composite material.
In order to achieve the purpose, the invention adopts the technical scheme that: a lithium battery composite material comprising a solid electrolyte and a metal mixed melt coating as a cathode coated on a surface of the solid electrolyte, the metal mixed melt coating being a mixed melt of metallic lithium, metallic zinc and lithium oxide.
According to the lithium battery composite material, the metal lithium, the metal zinc and the lithium oxide form a mixed melt and then are coated on the surface of the solid electrolyte to form the coating, so that the specific surface area difference between the cathode material and the contact surface of the solid electrolyte is reduced, the metal mixed melt coating containing the lithium metal is better attached to the surface of the solid electrolyte, a zinc-lithium alloy is formed in the metal mixed melt coating formed by the metal lithium, the metal zinc and the lithium oxide, an electron and lithium ion transmission channel can be formed, the utilization rate of lithium in a negative electrode is increased, meanwhile, the lithium oxide can be used as a buffer for expansion deformation of the negative electrode in the charging and discharging process, the lithium battery composite material has smaller impedance and conductivity, and the charging and discharging performance is better.
Preferably, the weight ratio of the metal lithium, the metal zinc and the lithium oxide is 10: (1-1.20): (1-1.20).
The inventor finds that when the weight ratio of the metal lithium, the metal zinc and the lithium oxide in the metal mixed melt coating which is used as the cathode and coated on the surface of the solid electrolyte is 10: (1-1.20): (1-1.20), the lithium battery composite material has lower impedance and better charge and discharge performance.
Preferably, the weight ratio of the metal lithium, the metal zinc and the lithium oxide is 10: (1-1.12): (1-1.12).
The inventor finds that when the weight ratio of metal lithium, metal zinc and lithium oxide in the metal mixed melt coating which is used as the cathode and coated on the surface of the solid electrolyte is 10: (1-1.12): (1-1.12), the lithium battery composite material has lower impedance and better charge and discharge performance.
Preferably, the weight ratio of the metal lithium, the metal zinc and the lithium oxide is 10: 1: 1.11.
the inventor finds that when the weight ratio of the metal lithium, the metal zinc and the lithium oxide in the metal mixed melt coating which is used as the cathode and coated on the surface of the solid electrolyte is 10: 1: 1.11, the lithium battery composite material has smaller impedance and better charge and discharge performance.
Preferably, the solid electrolyte is lithium lanthanum zirconium oxygen.
Preferably, the preparation method of the lithium battery composite material comprises the following steps:
(1) polishing the surface of the solid electrolyte, washing with an organic solvent, and drying;
(2) heating the metal lithium to 180-250 ℃ to obtain a metal lithium melt A;
(3) adding metal zinc and lithium oxide into the metal lithium melt A, and stirring at 180-250 ℃ to obtain a metal mixed melt B;
(4) and (4) coating the metal mixed melt B obtained in the step (3) on the surface of a solid electrolyte to form a metal mixed melt coating, thus obtaining the lithium battery composite material.
Preferably, in the step (2), the metallic lithium is heated to 200 ℃ to obtain the metallic lithium melt a.
The invention also provides a lithium battery comprising a lithium battery composite material as described in any of the above.
The lithium battery has better charge and discharge performance by applying any one of the lithium battery composite materials.
The invention has the beneficial effects that: the invention provides a lithium battery composite material, which is characterized in that metal lithium, metal zinc and lithium oxide form a mixed melt and then are coated on the surface of a solid electrolyte to form a coating, so that the specific surface area difference between a cathode material and the contact surface of the solid electrolyte is reduced, the metal mixed melt coating containing lithium metal is better attached to the surface of the solid electrolyte, a zinc-lithium alloy is formed in the metal mixed melt coating formed by the metal lithium, the metal zinc and the lithium oxide, and can form an electron and lithium ion transmission channel to increase the utilization rate of lithium in a negative electrode, and the lithium oxide can be used as a buffer of expansion deformation of the negative electrode in the charging and discharging process, so that the lithium battery composite material has lower impedance and conductivity and better charging and discharging performance.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a lithium battery composite material according to an example of the present invention and a comparative example.
Fig. 2 is a graph showing the characteristic properties of lithium battery composites of examples and comparative examples of the present invention.
Fig. 3 is an ac impedance spectrum of the lithium battery composite materials of the examples and comparative examples of the present invention.
Fig. 4 is a graph showing charge and discharge performance of lithium battery composites according to examples of the present invention and comparative examples.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The lithium battery composite material comprises a solid electrolyte and a metal mixed melt coating as a cathode, wherein the metal mixed melt coating is coated on the surface of the solid electrolyte, the metal mixed melt coating is a mixed melt of metal lithium, metal zinc and lithium oxide, and the weight ratio of the metal lithium to the metal zinc to the lithium oxide is 10: 1: 1, the solid electrolyte is lithium lanthanum zirconium oxygen (LLZTO).
The preparation method of the lithium battery composite material of the embodiment comprises the following steps:
(1) polishing the surface of lithium lanthanum zirconium oxide solid electrolyte with the diameter of 1cm and the thickness of 1mm by using 2000-mesh abrasive paper, washing by using ethanol, and drying;
(2) heating 0.183g of metallic lithium to 200 ℃ to obtain a metallic lithium melt A;
(3) adding 0.0183g of metal zinc and 0.0183g of lithium oxide into the metal lithium melt A, stirring at 200 ℃ until white powder completely disappears, and removing surface impurities to obtain a metal mixed melt B;
(4) and (4) coating the metal mixed melt B obtained in the step (3) on the surface of a solid electrolyte to form a metal mixed melt coating, and cooling to obtain the lithium battery composite material.
Example 2
As a lithium battery composite material according to an embodiment of the present invention, the only differences between this embodiment and embodiment 1 are: the weight ratio of the metal lithium to the metal zinc to the lithium oxide is 10: 1.11: 1.
example 3
As a lithium battery composite material according to an embodiment of the present invention, the only differences between this embodiment and embodiment 1 are: the weight ratio of the metal lithium to the metal zinc to the lithium oxide is 10: 1: 1.11.
comparative example 1
A lithium battery composite as a comparative example of the present invention, which comprises a solid electrolyte and a metal mixed melt coating layer coated on a surface of the solid electrolyte as a cathode, the metal mixed melt coating layer being a mixed melt of metallic lithium and zinc oxide, the weight ratio of the metallic lithium to the zinc oxide being 10: 1, the solid electrolyte is lithium lanthanum zirconium oxygen (LLZTO).
The preparation method of the lithium battery composite material of the comparative example includes the steps of:
(1) polishing the surface of lithium lanthanum zirconium oxide solid electrolyte with the diameter of 1cm and the thickness of 1mm by using 2000-mesh abrasive paper, washing by using ethanol, and drying;
(2) heating 0.183g of metallic lithium to 200 ℃ to obtain a metallic lithium melt A;
(3) adding 0.0183g of zinc oxide into the metal lithium melt A, stirring at 200 ℃ until white powder completely disappears, and removing surface impurities to obtain a metal mixed melt B;
(4) and (4) coating the metal mixed melt B obtained in the step (3) on the surface of a solid electrolyte to form a metal mixed melt coating, and cooling to obtain the lithium battery composite material.
Comparative example 2
A lithium battery composite as a comparative example of the present invention, which comprises a solid electrolyte and a metal mixed melt coating layer coated on a surface of the solid electrolyte as a cathode, the metal mixed melt coating layer being a mixed melt of metallic lithium and metallic zinc, the weight ratio of the metallic lithium to the metallic zinc being 10: 1.11, the solid electrolyte is lithium lanthanum zirconium oxygen (LLZTO).
The preparation method of the lithium battery composite material of the comparative example includes the steps of:
(1) polishing the surface of lithium lanthanum zirconium oxide solid electrolyte with the diameter of 1cm and the thickness of 1mm by using 2000-mesh abrasive paper, washing by using ethanol, and drying;
(2) heating 0.183g of metallic lithium to 200 ℃ to obtain a metallic lithium melt A;
(3) adding 0.0203g of metallic zinc into the metallic lithium melt A, stirring at 200 ℃ until white powder completely disappears, and removing surface impurities to obtain a metallic mixed melt B;
(4) and (4) coating the metal mixed melt B obtained in the step (3) on the surface of a solid electrolyte to form a metal mixed melt coating, and cooling to obtain the lithium battery composite material.
Comparative example 3
A lithium battery composite as a comparative example of the present invention, comprising a solid electrolyte and a metal melt coating applied on a surface of the solid electrolyte as a cathode, the metal melt coating being a metal lithium melt, and the solid electrolyte being lithium lanthanum zirconium oxygen (LLZTO).
The preparation method of the lithium battery composite material of the comparative example includes the steps of:
(1) polishing the surface of lithium lanthanum zirconium oxide solid electrolyte with the diameter of 1cm and the thickness of 1mm by using 2000-mesh abrasive paper, washing by using ethanol, and drying;
(2) heating 0.183g of metallic lithium to 200 ℃ to obtain a metallic lithium melt A;
(3) and (3) coating the metal mixed melt A obtained in the step (2) on the surface of a solid electrolyte to form a metal melt coating, and cooling to obtain the lithium battery composite material.
Effect example 1
The lithium battery composite materials prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to scanning electron microscopy, X-ray diffraction analysis, and charge and discharge performance tests.
As shown in fig. 1, fig. 1(a) is a Scanning Electron Microscope (SEM) image of a lithium battery composite material of comparative example 1, fig. 1(b) is a Scanning Electron Microscope (SEM) image of a lithium battery composite material of comparative example 2, fig. 1(c) is a Scanning Electron Microscope (SEM) image of a lithium battery composite material of comparative example 3, fig. 1(d) is a Scanning Electron Microscope (SEM) image of a lithium battery composite material of example 1, fig. 1(e) is a Scanning Electron Microscope (SEM) image of a lithium battery composite material of example 2, and fig. 1(f) is a Scanning Electron Microscope (SEM) image of a lithium battery composite material of example 3. As can be seen from fig. 1, the roughness of the lithium battery composite materials of examples 1 to 3 is better than that of the lithium battery composite materials of comparative examples 1 to 3, which shows that the current density of the lithium battery composite material can be reduced and the formation of lithium dendrites can be alleviated by combining lithium oxide, zinc and lithium to form a metal mixed melt coating and spreading the metal mixed melt coating on the surface of a solid electrolyte.
As shown in fig. 2, fig. 2(a) is an actual view of comparative example 3, and it can be seen from fig. 2(a) that the metallic lithium melt of comparative example 3 does not spread on the surface of the solid electrolyte sheet, fig. 2(b) is an actual view of example 3, fig. 2(c) is an SEM image of the lithium battery composite material of example 3, and fig. 2(d) is an infrared diffraction XRD image of the lithium battery composite material of example 3. Fig. 2(b) shows that the lithium battery composite material of example 3 contains lithium-zinc alloy, lithium oxide and metallic lithium, and fig. 2(c) and 2(d) illustrate that a metal mixed melt coating (Li-ZnO) formed of metallic lithium, metallic zinc and lithium oxide can be laid on the surface of the solid electrolyte (LLZTO) and tightly fit on the solid electrolyte. It can be seen from fig. 2(d) that the contact interface of the metal mixed melt coating layer and the solid electrolyte in the lithium battery composite material of example 3 has no voids.
As shown in fig. 3, fig. 3(a) is an ac impedance diagram of the lithium battery composite material of comparative example 1, fig. 3(b) is an ac impedance diagram of the lithium battery composite material of comparative example 2, fig. 3(c) is an ac impedance diagram of the lithium battery composite material of comparative example 3, fig. 3(d) is an ac impedance diagram of the lithium battery composite material of example 1, fig. 3(e) is an ac impedance diagram of the lithium battery composite material of example 2, and fig. 3(f) is an ac impedance diagram of the lithium battery composite material of example 3. The lithium battery composite material of comparative example 1 had an interfacial ion transfer resistance of 125. omega. cm -2 The lithium battery composite material of comparative example 2 had an interfacial ion transfer resistance of 250. omega. cm -2 The interface ion transfer impedance of the lithium battery composite material of comparative example 3 was 2319. omega. cm -2 The interfacial ion transfer resistance of the lithium battery composite material of example 1 was 80. omega. cm -2 The interfacial ion transfer resistance of the lithium battery composite material of example 2 was 85. omega. cm -2 The interfacial ion transfer resistance of the lithium battery composite material of example 3 was 35. omega. cm -2 The interfacial ion transfer resistance of the lithium battery composites of examples 1-3 is much lower than that of the lithium battery composites of comparative examples 1-3, which shows that the alternating current resistance of the lithium battery composites can be reduced by combining lithium oxide, zinc and lithium to form a metal mixed melt coating and flatly laying the metal mixed melt coating on the surface of a solid electrolyte. Also, comparative examples 1-3 found that the ac impedance of example 3 was relatively lower, indicating that the weight ratio of metallic lithium, metallic zinc and lithium oxide was 10: 1: 1.11 the interfacial ion transfer resistance of the lithium battery composite material is lower.
As shown in FIG. 4, FIG. 4(a) is a graph showing the charging and discharging performance of a pair electrode assembled from a lithium battery composite material of comparative example 1, FIG. 4(b) is a graph showing the charging and discharging performance of a pair electrode assembled from a lithium battery composite material of comparative example 2, FIG. 4(c) is a graph showing the charging and discharging performance of a pair electrode assembled from a lithium battery composite material of comparative example 3, FIG. 4(d) is a graph showing the charging and discharging performance of a pair electrode assembled from a lithium battery composite material of example 1, and FIG. 4(e) is a graph showing the charging and discharging performance of a pair electrode assembled from a lithium battery composite material of example 2Fig. 4(f) is a charge/discharge performance graph of a pair of electrodes assembled from the lithium battery composite material of example 3. As can be seen from FIG. 4, the current density was 0.1mA cm -2 The short circuit condition occurred in the electrode assembled with the lithium battery composite material of comparative example 3 at the current density of (1), comparative example 3 and examples 1 to 3, which indicates that the electrode assembled with the lithium battery composite material of comparative example 3 cannot suppress the generation of lithium dendrite, the voltage of comparative example 1, comparative example 3 and examples 1 to 3 was maintained at about 0.02V, and when the current density was increased to 0.2mA cm -2 When the current density was increased to 0.2mA cm -2 When the voltage of the comparative example 1 and the comparative example 2 instantly reaches 0.12V, the fact that the interface of the lithium battery composite material of the comparative example 1 and the comparative example 2 also has large ion transmission resistance and corresponds to the result of the alternating current impedance spectrum is shown, and then the voltage gradually becomes smaller indicates that lithium dendrite starts to gradually generate into the lithium dendrite, so that the ion transmission distance becomes smaller and the apparent voltage becomes smaller. The voltage of the lithium battery composite material of the example 2 is gradually reduced from 0.04V, and fluctuation occurs, so that the counter electrode assembled by the lithium battery composite material of the example 2 is gradually short-circuited, and the voltage of the example 1 is jagged fluctuation, so that the electrode is short-circuited due to the growth of lithium dendrites. Example 3 the voltage was relatively stable, demonstrating that the lithium battery composite of example 3 was most effective in suppressing lithium dendrites.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A lithium battery composite material, which is characterized by comprising a solid electrolyte and a metal mixed melt coating as a negative electrode, wherein the metal mixed melt coating is a mixed melt of metal lithium, metal zinc and lithium oxide; the weight ratio of the metal lithium to the metal zinc to the lithium oxide is 10: (1-1.20): (1-1.20).
2. The lithium battery composite material as claimed in claim 1, wherein the weight ratio of the metallic lithium, the metallic zinc and the lithium oxide is 10: (1-1.12): (1-1.12).
3. The lithium battery composite material as claimed in claim 1, wherein the weight ratio of the metallic lithium, the metallic zinc and the lithium oxide is 10: 1: 1.11.
4. the lithium battery composite of claim 1, wherein the solid state electrolyte is lithium lanthanum zirconium oxygen.
5. The lithium battery composite material as claimed in claim 1, wherein the preparation method of the lithium battery composite material comprises the steps of:
(1) polishing the surface of the solid electrolyte, washing with an organic solvent, and drying;
(2) heating the metal lithium to 180-250 ℃ to obtain a metal lithium melt A;
(3) adding metal zinc and lithium oxide into the metal lithium melt A, and stirring at 180-250 ℃ to obtain a metal mixed melt B;
(4) and (4) coating the metal mixed melt B obtained in the step (3) on the surface of a solid electrolyte to form a metal mixed melt coating, so as to obtain the lithium battery composite material.
6. The lithium battery composite material as claimed in claim 5, wherein in the step (2), the metallic lithium is heated to 200 ℃ to obtain the metallic lithium melt A.
7. A lithium battery, characterized in that it comprises a lithium battery composite as claimed in any one of claims 1 to 6.
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CN1989649A (en) * | 2004-07-26 | 2007-06-27 | 原子能委员会 | Electrode for a lithium battery method for production of such an electrode and lithium battery comprising said electrode |
CN108110217A (en) * | 2017-12-19 | 2018-06-01 | 成都亦道科技合伙企业(有限合伙) | A kind of solid state lithium battery composite negative pole and preparation method thereof |
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CN1989649A (en) * | 2004-07-26 | 2007-06-27 | 原子能委员会 | Electrode for a lithium battery method for production of such an electrode and lithium battery comprising said electrode |
CN108110217A (en) * | 2017-12-19 | 2018-06-01 | 成都亦道科技合伙企业(有限合伙) | A kind of solid state lithium battery composite negative pole and preparation method thereof |
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