CN111834620A - Lithium metal battery positive electrode, lithium metal battery and preparation method thereof - Google Patents
Lithium metal battery positive electrode, lithium metal battery and preparation method thereof Download PDFInfo
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium metal battery anode which comprises an anode current collector and an anode active substance layer, wherein the anode active substance layer is formed by compounding anode slurry on at least one surface of the anode current collector, and the anode slurry comprises an anode active substance coated with first solid electrolyte particles, second solid electrolyte particles, a conductive agent and a binder. According to the invention, the first solid electrolyte particles are adopted to coat the positive active material, so that the thermal stability of the positive active material is improved. According to the invention, the second solid electrolyte particles are added into the positive electrode slurry and filled into the gaps among the positive electrode active materials coated by the first solid electrolyte particles, and after the liquid electrolyte is injected, the proportion of the positive electrode active material layer and the current collector to adsorb the liquid electrolyte can be reduced, so that the thermal stability and the safety of the lithium metal battery are improved.
Description
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to a lithium metal battery anode, a lithium metal battery and a preparation method thereof.
Background
The lithium ion battery is widely applied to various electronic devices and electric energy storage devices due to the characteristics of high working voltage, small self-discharge, no memory effect, environmental friendliness and the like. Especially, in the application of mobile phones, the energy density of the battery is required to be higher and higher due to the lighter and thinner mobile phones. In order to improve the energy density of the lithium ion battery, the key point is to search for a high-capacity positive and negative electrode active material. The theoretical specific capacity of the metallic lithium negative electrode is 3860mAh/g, the voltage platform is-3.04V (vs standard hydrogen electrode), and the metallic lithium negative electrode has excellent conductivity and is very suitable for being used as the negative electrode of a high-energy-density battery. The main problem which troubles the lithium metal cathode is mainly the problem of lithium dendrite, in the circulation process, because of the local polarization factor, the lithium dendrite grows on the surface of the lithium metal, and when the lithium dendrite grows to a certain degree, the lithium dendrite can penetrate through a diaphragm, so that the safety problem is caused. In order to improve the safety of lithium metal batteries, solid-state batteries are one major direction. However, the interfacial compatibility of the solid electrolyte with the lithium metal battery is poor, resulting in poor cycle performance of the lithium metal battery.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: in view of the disadvantages of the prior art, a lithium metal battery positive electrode is provided, which can improve the thermal stability of a positive electrode active material and the safety of a lithium metal battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a lithium metal battery positive pole, includes anodal mass flow body and anodal active material layer, anodal active material layer is in by anodal thick liquids complex an at least surface of anodal mass flow body forms, anodal thick liquids include anodal active material, second solid electrolyte granule, conducting agent and the binder that the cladding has first solid electrolyte granule.
The first solid electrolyte particles are made of solid electrolyte materials with high lithium ion conductivity and good thermal stability, and after the first solid electrolyte particles are coated, the specific capacity of the positive active material is not limited, and the high-temperature cycle life of the positive active material can be prolonged.
The positive active material is a material capable of reversibly releasing and inserting lithium ions and comprises at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, lithium nickel manganese, lithium manganese iron phosphate, lithium cobalt phosphate and a lithium-rich manganese group. The positive electrode current collector includes, but is not limited to, aluminum foil.
The conductive agent includes at least one of conductive carbon black, conductive graphite, conductive carbon fiber, carbon nanotube, and graphene. The conductive agent includes, but is not limited to, the above-mentioned ones, and is a common conductive agent for lithium ion batteries.
The binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylpyrrolidone, polypropylene, polyethylene, polyurethane and polyamide. The binder includes, but is not limited to, the above binders, which are commonly used in lithium ion batteries.
The method for coating the positive active material with the first solid electrolyte particles includes, but is not limited to, a radio frequency magnetron sputtering method, a coating machine coating method or a sintering method after preparing a precursor.
As an improvement of the positive electrode for a lithium metal battery according to the present invention, the first solid electrolyte particles are crystalline oxide solid electrolyte particles. This is because the reduction potential of the oxide solid electrolyte is generally greater than 3V, which can satisfy the existing demand. And the crystalline oxide solid electrolyte is insensitive to water vapor in the air, is not easy to absorb moisture in the air, and can avoid safety accidents caused by the reaction of the moisture and the lithium metal. It should be noted that the first solid electrolyte particles cannot be amorphous oxide solid electrolyte particles, because amorphous oxide solid electrolyte particles are sensitive to moisture in the air and easily absorb moisture in the air, and lithium metal can ignite or even explode when it contacts water. The first solid electrolyte particles cannot be selected as the sulfide solid electrolyte particles because the electrochemical stability window of the sulfide solid electrolyte is low, typically below 3V. The first solid electrolyte particles cannot be selected from polymer solid electrolytes because they need to have good ionic conductivity at high temperatures.
As an improvement of the positive electrode for a lithium metal battery according to the present invention, the oxide solid electrolyte particles include at least one of garnet-type oxide solid electrolyte particles, perovskite-type oxide solid electrolyte particles, and NASICON-type oxide solid electrolyte particles. The first solid electrolyte particle is an oxide solid electrolyte of NASICON type because it can form a stable composite structure after coating the positive electrode active material.
As an improvement of the positive electrode for a lithium metal battery according to the present invention, the oxide solid electrolyte particles include at least one of lithium lanthanum titanium oxide, lithium lanthanum zirconium oxide, and lithium titanium aluminum phosphate. Wherein Lithium Lanthanum Titanium Oxide (LLTO) is perovskite type oxide solid electrolyte, Lithium Lanthanum Zirconium Oxide (LLZO) is garnet type solid electrolyte, and Lithium Aluminum Titanium Phosphate (LATP) is NASICON type solid electrolyte.
As an improvement of the lithium metal battery anode, the particle size of the second solid electrolyte particles is 1-1000 nm, and the second solid electrolyte particles are non-combustible solid electrolytes. Further, the particle size of the second solid electrolyte particles is preferably any value between 100nm and 1000nm, including but not limited to 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000 nm.
As an improvement of the positive electrode for a lithium metal battery according to the present invention, the second solid electrolyte particles include at least one of oxide solid electrolyte particles, sulfide solid electrolyte particles, and polymer solid electrolyte particles. The second solid electrolyte particles mainly serve to fill gaps between the positive electrode active materials coated with the first solid electrolyte particles, and after the liquid electrolyte is injected, the proportion of the positive electrode active material layer and the current collector adsorbing the liquid electrolyte can be reduced. Preferably, the second solid electrolyte particles are crystalline oxide solid electrolyte particles because crystalline oxide solid electrolyte particles are more air stable, less sensitive to water vapor and have a higher electrochemical stability window.
As an improvement of the positive electrode for a lithium metal battery according to the present invention, the mass ratio of the positive electrode active material coated with the first solid electrolyte, the second solid electrolyte particles, the conductive agent, and the binder is such that: the second solid electrolyte particles: the conductive agent: the binder is 86-97.4: 2-10: 0.1-2: 0.5 to 2.
It is another object of the present invention to provide a lithium metal battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the positive electrode is the positive electrode of the lithium metal battery described in any one of the above description, the electrolyte is an in-situ polymerized solid electrolyte, and the electrolyte comprises a lithium salt, an organic solvent, an additive, and an initiator. It should be noted that, compared with the solid electrolyte in the solid-state battery, the solid-state lithium-like battery can improve the wettability and stability of the interface, reduce the interface impedance, and make the battery have better rate performance and cycle life.
The diaphragm comprises any one of a polyethylene film, a polypropylene film, a polyethylene and polypropylene composite film, a polyimide film and a ceramic film. Preferably, the separator is a non-conducting solid electrolyte membrane.
The lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium bis (oxalato) borate (LiBOB), lithium bis (fluorosulfonylimide) (LiFSI), lithium bis (trifluoromethanesulfonylimide) (LiTFSI), lithium 4, 5-dicyano-2- (trifluoromethyl) isopyrazole (LiTDI) and lithium hexafluoroarsenate (LiAsF)6) At least one of (1). The lithium salt includes, but is not limited to, the above-mentioned ones, and is a lithium salt commonly used for lithium ion battery electrolytes.
The organic solvent comprises at least one of carbonate, carboxylic ester, fluoro carbonate, ether, fluoro ether and phosphazene. The organic solvent includes, but is not limited to, the above classes, and is an organic solvent commonly used for lithium ion battery electrolytes. Preferably, the carbonate organic solvent includes at least one of ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate and ethyl methyl carbonate, the carboxylic acid organic solvent includes at least one of propyl propionate, ethyl propionate, propyl acetate, butyl butyrate and ethyl butyrate, the ether and fluoroether organic solvent includes at least one of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, ethylene glycol dipropionitrile ether and octafluoropentyl-tetrafluoroethyl ether, and the phosphazene organic solvent includes at least one of ethoxypentafluorocyclotriphosphazene and hexachlorocyclotriphosphazene. The phosphazene organic solvent can also be used as a flame retardant additive.
The initiator includes azo type initiators or peroxide initiators. Azo initiators include azobisisobutyronitrile and the like, and peroxide initiators include dibenzoyl peroxide, ammonium persulfate and the like.
Wherein the lithium salt accounts for 10-15% of the total mass of the electrolyte, the organic solvent accounts for 82-87% of the total mass of the electrolyte, the additive accounts for 2.7-4.9% of the total mass of the electrolyte, and the initiator accounts for 0.1-0.3% of the total mass of the electrolyte.
The negative electrode comprises lithium metal, copper foil, nickel foil, stainless steel foil and any one of a carbon negative electrode or a silicon-carbon negative electrode with a CB value of 0-0.6. The CB value is an excess ratio of the negative electrode capacity to the positive electrode capacity per unit area.
As an improvement of the lithium metal battery of the present invention, the negative electrode includes a negative electrode current collector and a LiM alloy layer compounded on at least one surface of the negative electrode current collector, wherein M includes at least one of Mg, Zn, Ga, Bi, and Sn elements. Through the surface treatment of the negative electrode, a LiM alloy layer is compounded on the surface of the negative electrode current collector, so that the interface compatibility of the negative electrode and an electrolyte can be improved, the growth of lithium dendrite in the charging and discharging process is inhibited, and the cycle performance and the safety performance of the battery are improved. Further, the length of the LiM alloy layer is the same as the length of the negative electrode current collector, and the width of the LiM alloy layer is the same as the width of the negative electrode current collector. The thickness of the LiM alloy layer is 0.1 to 5 μm, because too thick a thickness affects the energy density of the lithium metal battery, and too thin a thickness is difficult to realize in practical production. Still further, the negative electrode current collector is lithium metal or a lithium alloy. At least one surface of the negative current collector is compounded with a thin LiM alloy layer, so that the direct contact between the lithium metal negative electrode and the electrolyte is prevented. Meanwhile, since the surface state of the lithium metal negative electrode is changed, the formation of lithium dendrites is also suppressed. Therefore, the cathode compounded with the LiM alloy layer can improve the interface compatibility of the lithium metal cathode and an electrolyte, and inhibit the growth of lithium dendrites in the charging and discharging processes, thereby improving the cycle performance and the safety performance of the battery.
As an improvement of the lithium metal battery of the present invention, the additive includes at least one of polyethylene glycol diacrylate, methyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, vinyl acetate, and vinyl sulfite. Preferably, the additive is a polymer monomer containing an unsaturated bond.
It is a further object of the present invention to provide a method for manufacturing a lithium metal battery as described in the foregoing description, comprising the operations of:
s1, mixing the lithium salt, the organic solvent, the additive and the initiator, and injecting the mixture into a bare cell obtained by laminating or winding the positive electrode, the negative electrode and the diaphragm;
s2, heating the bare cell at the temperature of 60-85 ℃ for 1-5 h to obtain an in-situ polymerized solid electrolyte, and packaging to obtain the lithium metal battery.
Compared with the prior art, the beneficial effects of the invention include but are not limited to: according to the invention, the first solid electrolyte particles are adopted to coat the positive active material, so that the thermal stability of the positive active material is improved. According to the invention, the second solid electrolyte particles are added into the positive electrode slurry and filled into the gaps among the positive electrode active materials coated by the first solid electrolyte particles, and after the liquid electrolyte is injected, the proportion of the positive electrode active material layer and the current collector to adsorb the liquid electrolyte can be reduced, so that the thermal stability and the safety of the lithium metal battery are improved.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. 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.
Example 1
The embodiment provides a lithium metal battery, and a preparation method thereof comprises the following steps:
(1) preparation of the positive electrode:
s1, preparing a lithium cobaltate positive electrode active substance coated by the lithium titanium aluminum phosphate first solid electrolyte particles;
s2, coating lithium cobaltate positive electrode active material on lithium aluminum titanium phosphate first solid electrolyte particles, lithium aluminum titanium phosphate second solid electrolyte particles with the median particle size D50 of 500nm, CNTs (carbon nanotubes) and PVDF (polyvinylidene fluoride) according to the mass ratio of 92.0: 6.0: 1.0: 1.0, uniformly mixing, and then dispersing in N-methyl-2-pyrrolidone to obtain anode slurry; and uniformly coating the anode slurry on two sides of the aluminum foil, and rolling and cutting to obtain the lithium metal battery anode.
(2) Preparation of a negative electrode: the negative electrode is a lithium metal negative electrode.
(3) Preparing liquid mixed electrolyte: in a nitrogen-filled glove box (O)2＜2ppm，H2O is less than 3ppm), mixing ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate according to a mass ratio of 2: 2: 1: 5, uniformly mixing to prepare a non-aqueous organic solvent; then, a nonaqueous organic solvent accounting for 85% of the total mass of the electrolyte is taken, lithium hexafluorophosphate accounting for 10% of the total mass of the electrolyte, polyethylene glycol bisacrylamide accounting for 4.7% of the total mass of the electrolyte and azobisisobutyronitrile accounting for 0.3% of the total mass of the electrolyte are slowly added to prepare a lithium salt solution with the concentration of lithium hexafluorophosphate being 1.2mol/L, and the lithium salt solution is prepared into a liquid mixed electrolyte after being uniformly mixed.
(4) Preparing a lithium ion battery: baking the anode and the diaphragm (polyethylene film) of the lithium metal battery, stacking the anode, the diaphragm and the cathode in sequence to obtain a bare cell, encapsulating the bare cell by an aluminum plastic film, injecting electrolyte, heating the cell at 75 ℃ for 3h, carrying out in-situ polymerization reaction on the liquid mixed electrolyte to generate a solid electrolyte, standing, forming, shaping by a clamp, secondary sealing and carrying out capacity test to finish the preparation of the lithium metal battery.
Example 2
This example provides a lithium metal battery, different from example 1 in the preparation of an anode:
(2) preparation of a negative electrode: and uniformly paving the lithium-magnesium alloy with the thickness of 3 mu m on two surfaces of the lithium metal negative electrode, and pressing the lithium-magnesium alloy and the lithium metal negative electrode together by rolling to obtain the modified lithium metal negative electrode.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
This example provides a lithium metal battery, which is different from example 1 in the preparation of a positive electrode of the lithium metal battery,
s1, preparing a lithium lanthanum zirconium oxide first solid electrolyte particle coated lithium cobaltate positive electrode active material;
s2, coating lithium lanthanum zirconium oxide first solid electrolyte particles with lithium cobalt oxide positive active materials, lithium lanthanum zirconium oxide second solid electrolyte particles with the median diameter D50 of 500nm, CNTs (carbon nanotubes) and PVDF (polyvinylidene fluoride) according to the mass ratio of 86.0: 10.0: 2.0: 2.0, uniformly mixing, and then dispersing in N-methyl-2-pyrrolidone to obtain anode slurry; and uniformly coating the anode slurry on two sides of the aluminum foil, and rolling and cutting to obtain the lithium metal battery anode.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
This example provides a lithium metal battery, which is different from example 1 in the preparation of a positive electrode of the lithium metal battery,
s1, preparing lithium lanthanum titanium oxide first solid electrolyte particle coated lithium cobaltate positive electrode active material;
s2, coating lithium lanthanum titanium oxide first solid electrolyte particles with a lithium cobalt oxide positive electrode active material, lithium lanthanum titanium oxide second solid electrolyte particles with a median particle size D50 of 500nm, CNTs (carbon nanotubes) and PVDF (polyvinylidene fluoride) according to a mass ratio of 97.4: 2.0: 0.1: 0.5, uniformly mixing, and then dispersing in N-methyl-2-pyrrolidone to obtain anode slurry; and uniformly coating the anode slurry on two sides of the aluminum foil, and rolling and cutting to obtain the lithium metal battery anode.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
This example provides a lithium metal battery, which is different from example 1 in the preparation of a positive electrode of the lithium metal battery:
s1, preparing a lithium cobaltate positive electrode active substance coated by the lithium titanium aluminum phosphate first solid electrolyte particles;
s2, coating the lithium cobaltate positive electrode active material coated by the lithium aluminum titanium phosphate first solid electrolyte particles, the second solid electrolyte particles, CNTs (carbon nanotubes) and PVDF (polyvinylidene fluoride) according to a mass ratio of 92: 6.0: 1.0: 1.0, uniformly mixing, and then dispersing in N-methyl-2-pyrrolidone to obtain anode slurry; and uniformly coating the anode slurry on two sides of the aluminum foil, and rolling and cutting to obtain the lithium metal battery anode.
The second solid electrolyte particles are lithium lanthanum zirconium oxide with the particle size of 500nm and lithium lanthanum titanium oxide with the particle size of 200nm, and the mass ratio of the lithium lanthanum zirconium oxide to the lithium lanthanum titanium oxide is 1: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
This example provides a lithium metal battery, which is different from example 1 in the preparation of a positive electrode of the lithium metal battery:
s1, preparing a lithium cobaltate positive electrode active substance coated by the lithium titanium aluminum phosphate first solid electrolyte particles;
s2, coating the lithium cobaltate positive electrode active material coated by the lithium aluminum titanium phosphate first solid electrolyte particles, the second solid electrolyte particles, CNTs (carbon nanotubes) and PVDF (polyvinylidene fluoride) according to a mass ratio of 92: 6.0: 1.0: 1.0, uniformly mixing, and then dispersing in N-methyl-2-pyrrolidone to obtain anode slurry; and uniformly coating the anode slurry on two sides of the aluminum foil, and rolling and cutting to obtain the lithium metal battery anode.
Wherein, the second solid electrolyte particle is lithium lanthanum zirconium oxide with the particle size of 500nm, lithium lanthanum titanium oxide with the particle size of 100nm and lithium aluminum lithium phosphate with the particle size of 100nm, lithium lanthanum zirconium oxide: lithium lanthanum titanium oxide: the mass ratio of the lithium aluminum titanium phosphate is 1:1: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
This comparative example provides a lithium metal battery, and unlike example 1, the electrolyte is a solid electrolyte.
Comparative example 2
This comparative example provides a lithium metal battery, which is different from example 1 in the preparation of a positive electrode of the lithium metal battery:
lithium cobaltate positive electrode active material, titanium aluminum lithium phosphate second solid electrolyte particles with the median particle diameter D50 of 500nm, CNTs (carbon nanotubes) and PVDF (polyvinylidene fluoride) are mixed according to the mass ratio of 92: 6.0: 1.0: 1.0, uniformly mixing, and then dispersing in N-methyl-2-pyrrolidone to obtain anode slurry; and uniformly coating the anode slurry on two sides of the aluminum foil, and rolling and cutting to obtain the lithium metal battery anode.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 3
This comparative example provides a lithium metal battery, which is different from example 1 in the preparation of a positive electrode of the lithium metal battery:
s1, preparing a lithium cobaltate positive electrode active substance coated by the lithium titanium aluminum phosphate first solid electrolyte particles;
s2, coating lithium cobaltate positive electrode active material coated by lithium aluminum titanium phosphate first solid electrolyte particles, CNTs (carbon nanotubes) and PVDF (polyvinylidene fluoride) according to the mass ratio of 96: 2.0: 2.0, uniformly mixing, and then dispersing in N-methyl-2-pyrrolidone to obtain anode slurry; and uniformly coating the anode slurry on two sides of the aluminum foil, and rolling and cutting to obtain the lithium metal battery anode.
The rest is the same as embodiment 1, and the description is omitted here.
The lithium metal batteries prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to a thermal shock test, a nail penetration test, and a cycle performance test, respectively, and the test results are shown in table 1.
TABLE 1
As can be seen from example 1 and comparative example 1, the lithium ion battery with the electrolyte as the solid-state electrolyte has better cycle performance than the lithium ion battery with the electrolyte as the pure solid-state electrolyte, because the solid-state electrolyte can improve the interface compatibility between the negative electrode and the electrolyte, thereby improving the cycle performance of the battery.
As can be seen from example 1 and comparative example 2, the high-temperature cycle life and thermal stability of the positive electrode active material can be significantly improved after the positive electrode active material of example 1 is coated with the first solid electrolyte particles.
As can be seen from example 1 and comparative example 3, in example 1, the second solid electrolyte particles are added to the positive electrode slurry and filled in the gaps between the positive electrode active materials coated with the first solid electrolyte particles, and after the liquid electrolyte is injected, the ratio of the positive electrode active material layer to the current collector to adsorb the liquid electrolyte can be reduced, thereby improving the thermal stability and safety of the lithium metal battery.
As can be seen from examples 1 and 2, the cycle performance and safety performance of example 2 are better because the lithium metal battery negative electrode is compounded with a LiM alloy layer on the surface thereof, which can prevent the lithium metal negative electrode from directly contacting the electrolyte. Meanwhile, since the surface state of the lithium metal negative electrode is changed, the formation of lithium dendrites is also suppressed. Therefore, the lithium metal cathode compounded with the LiM alloy layer can improve the interface compatibility of the lithium metal cathode and an electrolyte, and inhibit the growth of lithium dendrites in the charging and discharging processes, thereby improving the cycle performance and the safety performance of the battery.
As can be seen from examples 1 and 5 to 6, the heat resistance stability of the battery can be further improved because the second solid electrolyte particles have different particle diameters, and the second solid electrolyte particles can be sufficiently filled in the gaps between the positive electrode active materials coated by the first solid electrolyte particles, and after the liquid electrolyte is injected, the proportion of the positive electrode active material layer and the current collector to adsorb the liquid electrolyte can be further reduced, so that the heat stability and the safety of the lithium metal battery can be improved.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The utility model provides a lithium metal battery positive pole, its characterized in that includes anodal mass flow body and anodal active material layer, anodal active material layer is in by anodal thick liquids complex anodal mass flow body's at least one surface forms, anodal thick liquids include the anodal active material, the solid-state electrolyte granule of second, conductive agent and the binder of cladding first solid-state electrolyte granule.
2. The lithium metal battery positive electrode of claim 1, wherein the first solid electrolyte particles are crystalline oxide solid electrolyte particles.
3. The lithium metal battery positive electrode of claim 2, wherein the oxide solid electrolyte particles comprise at least one of garnet-type oxide solid electrolyte particles, perovskite-type oxide solid electrolyte particles, and NASICON-type oxide solid electrolyte particles.
4. The lithium metal battery positive electrode of claim 3, wherein the oxide solid state electrolyte particles comprise at least one of lithium lanthanum titanium oxygen, lithium lanthanum zirconium oxygen, and lithium titanium aluminum phosphate.
5. The positive electrode for a lithium metal battery according to claim 1, wherein the second solid electrolyte particles have a particle size of 1 to 1000nm, and the second solid electrolyte particles are a non-combustible solid electrolyte.
6. The lithium metal battery positive electrode of claim 1, wherein the second solid electrolyte particles comprise at least one of oxide solid electrolyte particles, sulfide solid electrolyte particles, and polymer solid electrolyte particles.
7. The positive electrode for a lithium metal battery according to claim 1, wherein the positive electrode active material coated with a first solid electrolyte, the second solid electrolyte particles, the conductive agent, and the binder are present in a mass ratio of the positive electrode active material coated with a first solid electrolyte: the second solid electrolyte particles: the conductive agent: the binder is 86-97.4: 2-10: 0.1-2: 0.5 to 2.
8. A lithium metal battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the positive electrode is the lithium metal battery positive electrode according to any one of claims 1 to 7, the electrolyte is an in-situ polymerized solid-like electrolyte, and the electrolyte comprises a lithium salt, an organic solvent, an additive, and an initiator.
9. The lithium metal battery of claim 8, wherein the negative electrode comprises a negative electrode current collector and a LiM alloy layer composited on at least one surface of the negative electrode current collector, wherein M comprises at least one of Mg, Zn, Ga, Bi, and Sn elements.
10. A method for preparing a lithium metal battery according to claim 8, comprising the following operations:
s1, mixing the lithium salt, the organic solvent, the additive and the initiator, and injecting the mixture into a bare cell obtained by laminating or winding the positive electrode, the negative electrode and the diaphragm;
s2, heating the bare cell at the temperature of 60-85 ℃ for 1-5 h to obtain an in-situ polymerized solid electrolyte, and packaging to obtain the lithium metal battery.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112687948A (en) * | 2020-12-22 | 2021-04-20 | 双登集团股份有限公司 | Solid-state battery with improved interface performance and preparation method thereof |
| CN112786832A (en) * | 2021-01-25 | 2021-05-11 | 湖南立方新能源科技有限责任公司 | Negative plate and lithium ion battery |
| CN113793976A (en) * | 2021-09-08 | 2021-12-14 | 远景动力技术(江苏)有限公司 | Semi-solid lithium ion battery and preparation method thereof |
| CN114122317A (en) * | 2021-11-23 | 2022-03-01 | 蜂巢能源科技(无锡)有限公司 | Positive pole piece for solid-state battery and preparation method and application thereof |
| CN114784247A (en) * | 2022-04-06 | 2022-07-22 | 鸿海精密工业股份有限公司 | Battery positive electrode material and method for producing same |
| CN114784223A (en) * | 2022-04-28 | 2022-07-22 | 广东马车动力科技有限公司 | Positive plate and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932225A (en) * | 2016-06-29 | 2016-09-07 | 中国科学院青岛生物能源与过程研究所 | Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery |
| CN106232526A (en) * | 2014-04-24 | 2016-12-14 | 第稀元素化学工业株式会社 | The manufacture method of garnet type compound and garnet type compound, and all solid lithium secondary battery containing this garnet type compound |
| CN106654353A (en) * | 2016-11-25 | 2017-05-10 | 清华大学深圳研究生院 | Gel polymer electrolyte power battery |
| CN107039634A (en) * | 2017-05-04 | 2017-08-11 | 北京科技大学 | Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method |
| CN107591536A (en) * | 2017-09-02 | 2018-01-16 | 清陶（昆山）能源发展有限公司 | Gel anode composite piece and preparation method thereof and the method for preparing solid lithium battery |
| CN108963222A (en) * | 2018-07-13 | 2018-12-07 | 国联汽车动力电池研究院有限责任公司 | Solid union electrolyte-electrode active material and the preparation method and application thereof |
| CN109390587A (en) * | 2017-08-11 | 2019-02-26 | 天津中能锂业有限公司 | All-solid-state battery cathode, preparation method and all-solid-state battery |
| CN110048153A (en) * | 2019-05-06 | 2019-07-23 | 浙江大学 | A kind of solid metallic lithium battery and preparation method thereof |
| CN110429329A (en) * | 2019-08-15 | 2019-11-08 | 湖南立方新能源科技有限责任公司 | A kind of preparation method and all-solid sodium ion battery of all-solid sodium ion battery |
-
2020
- 2020-06-24 CN CN202010583755.4A patent/CN111834620A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106232526A (en) * | 2014-04-24 | 2016-12-14 | 第稀元素化学工业株式会社 | The manufacture method of garnet type compound and garnet type compound, and all solid lithium secondary battery containing this garnet type compound |
| CN105932225A (en) * | 2016-06-29 | 2016-09-07 | 中国科学院青岛生物能源与过程研究所 | Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery |
| CN106654353A (en) * | 2016-11-25 | 2017-05-10 | 清华大学深圳研究生院 | Gel polymer electrolyte power battery |
| CN107039634A (en) * | 2017-05-04 | 2017-08-11 | 北京科技大学 | Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method |
| CN109390587A (en) * | 2017-08-11 | 2019-02-26 | 天津中能锂业有限公司 | All-solid-state battery cathode, preparation method and all-solid-state battery |
| CN107591536A (en) * | 2017-09-02 | 2018-01-16 | 清陶（昆山）能源发展有限公司 | Gel anode composite piece and preparation method thereof and the method for preparing solid lithium battery |
| CN108963222A (en) * | 2018-07-13 | 2018-12-07 | 国联汽车动力电池研究院有限责任公司 | Solid union electrolyte-electrode active material and the preparation method and application thereof |
| CN110048153A (en) * | 2019-05-06 | 2019-07-23 | 浙江大学 | A kind of solid metallic lithium battery and preparation method thereof |
| CN110429329A (en) * | 2019-08-15 | 2019-11-08 | 湖南立方新能源科技有限责任公司 | A kind of preparation method and all-solid sodium ion battery of all-solid sodium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| 王长宏等: "《新能源汽车技术现状与应用前景》", 31 May 2015, 广东经济出版社 * |
| 连芳: "《电化学储能器件及关键材料》", 30 June 2019, 冶金工业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112687948A (en) * | 2020-12-22 | 2021-04-20 | 双登集团股份有限公司 | Solid-state battery with improved interface performance and preparation method thereof |
| CN112786832A (en) * | 2021-01-25 | 2021-05-11 | 湖南立方新能源科技有限责任公司 | Negative plate and lithium ion battery |
| CN113793976A (en) * | 2021-09-08 | 2021-12-14 | 远景动力技术(江苏)有限公司 | Semi-solid lithium ion battery and preparation method thereof |
| CN113793976B (en) * | 2021-09-08 | 2024-05-17 | 远景动力技术(江苏)有限公司 | Semi-solid lithium ion battery and preparation method thereof |
| CN114122317A (en) * | 2021-11-23 | 2022-03-01 | 蜂巢能源科技(无锡)有限公司 | Positive pole piece for solid-state battery and preparation method and application thereof |
| CN114122317B (en) * | 2021-11-23 | 2024-01-30 | 蜂巢能源科技(无锡)有限公司 | Positive electrode plate for solid-state battery and preparation method and application thereof |
| CN114784247A (en) * | 2022-04-06 | 2022-07-22 | 鸿海精密工业股份有限公司 | Battery positive electrode material and method for producing same |
| CN114784223A (en) * | 2022-04-28 | 2022-07-22 | 广东马车动力科技有限公司 | Positive plate and preparation method and application thereof |
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