CN105470466A - All-solid-state battery of skeleton supported alloy anode and preparation method thereof - Google Patents
All-solid-state battery of skeleton supported alloy anode and preparation method thereof Download PDFInfo
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- 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
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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
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- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an all-solid-state battery of a skeleton supported alloy anode and a preparation method thereof. The skeleton supported alloy anode material is higher in heat stability relative to metallic lithium; and moreover, after the treatment of a small amount of added inorganic solid electrolyte powder, when free Li in the gaps of lithium borate compound (Li7B6) particles on the surface layer of the alloy anode material is completely consumed, the transfer path of lithium ions can be maintained continuously because of the existence of the lithium ion conductor, and the disconnection problem of the transfer path of the lithium ions appearing between the anode and the electrolyte in the charging and discharging process of the all-solid-state battery is prevented. The skeleton supported alloy anode material is applied to the all-solid-state battery system, and a metallic lithium dead level on the anode side of the all-solid-state battery can be solved, so that the all-solid-state battery has the advantages of good cyclicity and high cycle efficiency (100%), and is extremely suitable for being applied to large-capacity all-solid-state batteries.
Description
Technical field
The invention belongs to technical field of chemical power, particularly relate to all-solid-state battery of a kind of skeletal support alloy anode and preparation method thereof.
Background technology
At present in lithium ion battery, owing to using the inflammable volatile organic liquid electrolyte such as ester class, ethers in a large number, lithium ion battery is made to be unsafe in essence.When battery is under the condition of abuse, the heat of battery can sharply rise moment, and electrolyte volatilizees in a large number and makes battery flatulence, or accumulation of heat reaches the ignition point of these organic solvents, causes the accidents such as the blast on fire of battery.In order to further promote the security performance of lithium ion battery, solve the leakage existing for conventional lithium battery system, flatulence and in particular cases burn, the safety issue such as blast, researcher proposes all multi-schemes, such as use flame-retardant additive, gel electrolyte and solid polyelectrolyte, these schemes can improve the security performance of lithium battery to a certain extent, but or cannot address this problem thoroughly.And adopt inorganic solid electrolyte to substitute organic electrolyte, at solution conventional lithium ion battery capacity while on the low side and useful life these two key issues partially short, be expected to the safety issue thoroughly solving battery, thus the solid lithium battery of solid electrolyte replacement traditional liquid organic electrolyte is just attracting increasing concern.In U.S., day, Ou Deng state power supply research and development route map, solid lithium battery is in occupation of very important status in accumulation power supply system of future generation, and each state all increases R&D intensity and input.
Solid lithium battery is a kind of solid electrolyte that adopts is the novel battery of ion conducting layer electric insulators, its advantage is except fail safe promotes, side reaction between electrode active material and electrolyte almost completely avoid, and makes all-solid-state battery have extraordinary cycle life in theory.In basic research, be all that " positive pole/electrolyte/negative pole " three layers of material are adopted high pressure integral forming method substantially during assembling solid lithium battery.Research finds, although this method can realize the circulation that all-solid-state battery carries out less cycle, when all-solid-state battery needs the circulation time carrying out tens cycles, the decay of this capacity will become clearly.And after cycle performance deterioration, battery roll is found the probability that lithium anode part comes off from solid electrolyte side is very large.The solid electrolyte adopted that the main cause of all-solid-state battery capacity attenuation is ascribed to solid lithium battery by us based on this is a kind of material of rigidity, negative pole lithium ceaselessly omnidirectional dissolving deposition in charge and discharge process, in addition the efflorescence consumption of lithium metal, make between electrolyte and lithium anode, to have occurred part dead level, this dead level makes solid lithium battery charge carrier bang path rupture, the internal resistance of cell increases gradually, and battery capacity decay also just obviously.Therefore, promote the cycle performance of all-solid-state battery, the lithium dead level problem existing for cathode of lithium side can not be ignored.
Lithium boron alloy is the Thermal Cell Cathode Material that a new generation has development prospect, and compared with Thermal Cell Cathode Material in the past, the lithium content of lithium boron alloy is the highest, and specific capacity is maximum, electrochemical potentials and pure lithium close, and more than 600 DEG C is still the advantage such as solid-state.Due in the process preparing lithium boron alloy, in the exothermic reaction that about 530 DEG C occur, generate the LiB compound (Li of skeletal structure
7b
6).Because Li
7b
6particle is originally as multi-pore structure, and bore hole size is less, and strong to the absorption affinity of Li, the free Li primary attachment in alloy is in these holes.
Summary of the invention
The object of this invention is to provide all-solid-state battery of a kind of skeletal support alloy anode and preparation method thereof, the preparation method of its alloy anode is simple, and in solid lithium battery system, result of use is obvious, is suitable for the large-scale production of solid lithium battery.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of all-solid-state battery of skeletal support alloy anode, comprises the following steps:
(1) preparation of skeletal support alloy anode: alloy material of cathode adopts Li-B alloy sheet, solid electrolyte adopts Li-La-Zr-O solid electrolyte powder, Li-B alloy electrode plate surface passivation layer film is polished off, be the Li-La-Zr-O solid electrolyte powder of 30-300 micron by particle diameter, according to 0.1-1.5mg/cm
2uniform application is on Li-B alloy electrode plate surface, and powder covers on it by the pressure then applying 5-15MPa, obtains the skeletal support alloy material of cathode of electrolyte treatment;
(2) preparation of composite electrolyte: the molecular weight of the organic principle employing of composite electrolyte is polyethylene glycol polymer PEO or the plastic crystal type organic succinonitrile SN of 6000-50 ten thousand, solvent is tetrahydrofuran THF, and electrolyte is two (trimethyl fluoride sulfonyl) imine lithium LiTFSI; The inorganic constituents of composite electrolyte is that particle size is less than 300 object Li-Al-Ge-P powder or Li-Al-Ti-P powder; Preparation method is as follows:
Be (4-16) in EO segment and Li ion according to mol ratio: 1 ratio takes PEO and LiTFSI, adds THF and is dissolved, 30-90 DEG C of stirring under inert atmosphere, and by mass percentage, solid content is the solution of 1-10% in configuration; According to mass ratio (PEO+LiTFSI): Li-Al-Ge (Ti)-P powder=1:(3-49), add Li-Al-Ge (Ti)-P powder, by its mixing and stirring, obtain the slurry of composite solid electrolyte; Or SN is dissolved at the temperature of 50 DEG C, then add LiTFSI, be mixed with the solution of 0.2-1.0mol/L; According to mass ratio (SN+LiTFSI): Li-Al-Ge (Ti)-P powder=1:(3-49), add Li-Al-Ge (Ti)-P powder, by its mixing and stirring, obtain the mixture of composite solid electrolyte;
(3) assembling of all-solid-state battery: the lithium alloy electrode sheet surface of the process that the slurry uniform application of composite solid electrolyte step (2) prepared obtains in step (1), then to spend the night at 50-100 DEG C oven dry, by the lithium alloy electrode sheet being coated with composite electrolyte of oven dry under the pressure of 5-20MPa, composite electrolyte is covered smooth, cover on composite electrolyte by the anode electrode sheet processed, assembling obtains all-solid-state battery.
In described step (1), the particle diameter of Li-La-Zr-O solid electrolyte powder is 100 microns, according to 0.5mg/cm
2all with spread upon Li-B alloy electrode plate surface, powder covers on it by the pressure then applying 10MPa.
In described step (2), the molecular weight of PEO is 100,000; EO segment and Li ion are 8:1 according to molal weight ratio; According to mass ratio (PEO+LiTFSI): Li-Al-Ge (Ti)-P powder=1:19.
In described step (3), the process of anode electrode sheet: positive pole consist of active substance ferrous lithium phosphate LiFePO
4, binding agent Kynoar PVDF, conductive agent SP; Anode portion ionic conduction composition is polyethylene glycol polymer PEO, and the solvent dissolving PEO is THF, and electrolyte is LiTFSI; By active material LiFePO
4, the ratio of binding agent PVDF and conductive agent SP 8:1:1 in mass ratio applies into electrode, and after drying, cut-parts are for subsequent use; The PEO/LiTFSI solution prepared in step (2) is added drop-wise to anode electrode sheet surface, forms thin layer PEO/LiTFSI layer, oven dry of then it being spent the night at the temperature of 70 DEG C.
The all-solid-state battery of skeletal support alloy anode prepared by above-mentioned preparation method.
The advantage that the present invention has and good effect are:
1, the present invention is owing to adopting lithium boron alloy paper tinsel to be solid lithium battery negative material, and this negative material has Heat stability is good, compares with lithium metal, and lithium boron alloy reacts slowly in metal-air, compensate for the short slab of solid lithium battery security performance;
2, the lithium boron alloy paper tinsel of the present invention to skeletal structure processes, and a small amount of inorganic solid electrolyte powder of increase, makes alloy anode top layer LiB compound (Li
7b
6) when free Li runs out of in particle voids, the existence due to lithium ion conductor can continue the bang path maintaining lithium ion, prevents the open circuit in lithium ion mobility path;
3, the present invention adopts the solid lithium battery that the alloy anode of skeleton support is assembled, and has cyclicity good, and the advantage of cycle efficieny high (100%), is very suitable for the application in Large Copacity all-solid-state battery.
Accompanying drawing explanation
Fig. 1 is the cycle performance figure that the present invention uses the solid lithium battery of skeletal support alloy anode, and electrolyte ingredient is PEO/LiTFSI/Li-Al-Ge-P powder;
Fig. 2 for the present invention use the all-solid-state battery of skeletal support alloy anode under different current density corresponding to voltage capacity curve chart, electrolyte ingredient is PEO/LiTFSI/Li-Al-Ge-P powder;
Fig. 3 is the cycle performance figure that the present invention uses the solid lithium battery of skeletal support alloy anode, and electrolyte ingredient is PEO/LiTFSI/Li-Al-Ti-P powder;
Fig. 4 is that the present invention uses the all-solid-state battery of the skeletal support alloy anode corresponding voltage capacity curve chart of the 20th week, and electrolyte ingredient is PEO/LiTFSI/Li-Al-Ti-P powder;
Fig. 5 is the cycle performance figure that the present invention uses the solid lithium battery of skeletal support alloy anode, and electrolyte ingredient is SN/LiTFSI/Li-Al-Ti-P powder;
Fig. 6 uses the voltage capacity curve chart corresponding to all-solid-state battery the 40 cycle of skeletal support alloy anode for the present invention, and electrolyte ingredient is SN/LiTFSI/Li-Al-Ti-P powder.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby exemplify following examples, be described in detail as follows:
The preparation method of the all-solid-state battery of skeletal support alloy anode of the present invention, comprises the following steps:
(1) preparation of skeletal support alloy anode: alloy material of cathode adopts Li-B alloy sheet, solid electrolyte adopts Li-La-Zr-O solid electrolyte powder, Li-B alloy electrode plate surface passivation layer film is polished off, be the Li-La-Zr-O solid electrolyte powder of 30-300 micron by particle diameter, according to 0.1-1.5mg/cm
2uniform application is on Li-B alloy electrode plate surface, and powder covers on it by the pressure then applying 5-15MPa, obtains the skeletal support alloy material of cathode of electrolyte treatment;
(2) preparation of composite electrolyte: the molecular weight of the organic principle employing of composite electrolyte is polyethylene glycol polymer PEO or the plastic crystal type organic succinonitrile SN of 6000-50 ten thousand, solvent is tetrahydrofuran THF, and electrolyte is two (trimethyl fluoride sulfonyl) imine lithium LiTFSI; The inorganic constituents of composite electrolyte is that particle size is less than 300 object Li-Al-Ge-P powder or Li-Al-Ti-P powder; Preparation method is as follows:
Be (4-16) in EO segment and Li ion according to mol ratio: 1 ratio takes PEO and LiTFSI, adds THF and is dissolved, 30-90 DEG C of stirring under inert atmosphere, and by mass percentage, solid content is the solution of 1-10% in configuration; According to mass ratio (PEO+LiTFSI): Li-Al-Ge (Ti)-P powder=1:(3-49), add Li-Al-Ge (Ti)-P powder, by its mixing and stirring, obtain the slurry of composite solid electrolyte; Or
SN is dissolved at the temperature of 50 DEG C, then adds LiTFSI, be mixed with the solution of 0.2-1.0mol/L; According to mass ratio (SN+LiTFSI): Li-Al-Ge (Ti)-P powder=1:(3-49), add Li-Al-Ge (Ti)-P powder, by its mixing and stirring, obtain the mixture of composite solid electrolyte;
(3) assembling of all-solid-state battery: the lithium alloy electrode sheet surface of the process that the slurry uniform application of composite solid electrolyte step (2) prepared obtains in step (1), then to spend the night at 50-100 DEG C oven dry, by the lithium alloy electrode sheet being coated with composite electrolyte of oven dry under the pressure of 5-20MPa, composite electrolyte is covered smooth, cover on composite electrolyte by the anode electrode sheet processed, assembling obtains all-solid-state battery.
In described step (1), the particle diameter of Li-La-Zr-O solid electrolyte powder is 100 microns, according to 0.5mg/cm
2all with spread upon Li-B alloy electrode plate surface, powder covers on it by the pressure then applying 10MPa.
In described step (2), the molecular weight of PEO is 100,000; EO segment and Li ion are 8:1 according to molal weight ratio; According to mass ratio (PEO+LiTFSI): Li-Al-Ge (Ti)-P powder=1:19.
In described step (3), the process of anode electrode sheet: positive pole consist of active substance ferrous lithium phosphate LiFePO
4, binding agent Kynoar PVDF, conductive agent SP; Anode portion ionic conduction composition is polyethylene glycol polymer PEO, and the solvent dissolving PEO is THF, and electrolyte is LiTFSI; By active material LiFePO
4, the ratio of binding agent PVDF and conductive agent SP 8:1:1 in mass ratio applies into electrode, and after drying, cut-parts are for subsequent use; The PEO/LiTFSI solution that step (2) prepares is added drop-wise to anode electrode sheet surface, forms thin layer PEO/LiTFSI layer, oven dry of then it being spent the night at the temperature of 70 DEG C.
The all-solid-state battery of skeletal support alloy anode prepared by above-mentioned preparation method.
Embodiment 1
The preparation method of all-solid-state battery of the present invention, concrete technology contents is:
1, the preparation of alloy anode:
The alloy material of cathode adopted is Li-B alloy sheet, and the solid electrolyte adopted is Li-La-Zr-O system.
Concrete preparation process is as follows:
Cutting diameter is the Li-B alloy electrode plate of 1.8cm size, and is polished off by surface passivation layer film;
Get the Li-La-Zr-O solid electrolyte powder that 1mg particle size is 100 microns, and by its all with spread upon Li-B alloy electrode plate surface, powder covers on it by the pressure then applying 10MPa, obtains the alloy material of cathode of electrolyte treatment;
2, the preparation of composite electrolyte:
The PEO of the organic principle employing of composite electrolyte is the polymer of 100,000 molecular weight, and wherein adopt the solvent dissolving PEO to be THF, electrolyte is LiTFSI; The inorganic constituents of composite electrolyte is that particle size is less than 300 object Li-Al-Ge (Ti)-P powder.
Concrete preparation process is as follows:
Take PEO and LiTFSI (gross mass is about 800mg) in EO segment and Li ion 8:1 ratio, then adopt THF to be that solvent is dissolved, condition is that the temperature of lower 60 DEG C of inert atmosphere stirs, and solid content is 8%;
Take the solution 625mg prepared, and then take Li-Al-Ge (the Ti)-P powder of 950mg, by its mixing and stirring, obtain the slurry of composite solid electrolyte;
3, anode electrode preparation and process:
Positive pole consist of active material (LiFePO
4), binding agent (PVDF) and conductive agent (SP); Anode portion ionic conduction composition is PEO polymer, and wherein adopt the solvent dissolving PEO to be THF, electrolyte is LiTFSI.
Concrete preparation process is as follows:
By active material (LiFePO
4), binding agent (PVDF) and conductive agent (SP) apply into electrode in the ratio of 8:1:1 (mass ratio), and after drying, cut-parts are for subsequent use;
The PEO/LiTFSI solution prepared is added drop-wise to anode electrode sheet surface, forms thin layer PEO/LiTFSI layer, oven dry of then it being spent the night at the temperature of 70 DEG C;
4, the assembling of all-solid-state battery:
Adopt the Li-B alloy anode of the process of negative pole prepared by step 1, the composite electrolyte of electrolyte prepared by step 2 of employing, the LiFePO of the prepared also process of just very step 3 of employing
4positive pole.
Concrete preparation process is:
The Li-B alloy electrode plate surface of the process that the slurry uniform application of composite solid electrolyte step 2 prepared obtains in step 1, oven dry of then spending the night under the condition of 70 DEG C;
By the Li-B alloy electrode plate being coated with composite electrolyte of oven dry under the pressure of 10MPa, composite electrolyte is covered smooth;
The anode electrode sheet of step 3 gained is covered on composite electrolyte, and is adopted the button cell of 2032 models to assemble.
As shown in Figure 1, 2, the data of battery for obtaining in embodiments of the invention.
Embodiment 2
The preparation method of all-solid-state battery of the present invention, concrete technology contents is:
1, the preparation of alloy anode:
Identical with the alloy material of cathode preparation method used in embodiment 1.
2, the preparation of composite electrolyte:
The PEO of the organic principle employing of composite electrolyte is the polymer of 100,000 molecular weight, and wherein adopt the solvent dissolving PEO to be THF, electrolyte is LiTFSI; The inorganic constituents of composite electrolyte is that particle size is less than 300 object Li-Al-Ti-P powder.
Concrete preparation process is as follows:
Take PEO and LiTFSI (gross mass is about 800mg) in EO segment and Li ion 8:1 ratio, then adopt THF to be that solvent is dissolved, condition is that the temperature of lower 60 DEG C of inert atmosphere stirs, and solid content is 8%;
Take the solution 625mg prepared, and then take the Li-Al-Ti-P powder of 950mg, by its mixing and stirring, obtain the slurry of composite solid electrolyte;
3, anode electrode preparation and process:
With in embodiment 1 the anode electrode used preparation and processing mode identical.
4, the assembling of all-solid-state battery:
Mode with institute's all-solid-state battery assembling in embodiment 1 is identical.
As Fig. 3, shown in 4, be the data of battery obtained in embodiments of the invention.
Embodiment 3
The preparation method of all-solid-state battery of the present invention, concrete technology contents is:
1, the preparation of alloy anode:
Identical with the alloy material of cathode preparation method used in embodiment 1.
2, the preparation of composite electrolyte:
The organic principle of composite electrolyte adopts plastic crystal type organic succinonitrile (SN), and the electrolyte of employing is LiTFSI; The inorganic constituents of composite electrolyte is that particle size is less than 300 object Li-Al-Ge-P powder.
Concrete preparation process is as follows:
Dissolve at the temperature of succinonitrile 50 DEG C, then add LiTFSI, be mixed with the solution of 0.5mol/L;
Take the solution 50mg prepared, and then take the Li-Al-Ge-P powder of 950mg, by its mixing and stirring;
3, anode electrode preparation and process:
With in embodiment 1 the anode electrode used preparation and processing mode identical.
4, the assembling of all-solid-state battery:
Mode with institute's all-solid-state battery assembling in embodiment 1 is identical.
As Fig. 5, shown in 6, be the data of battery obtained in embodiments of the invention.
Above-described embodiment is only for illustration of technological thought of the present invention and feature, its object is to enable those skilled in the art understand content of the present invention and implement according to this, only can not limit the scope of the claims of the present invention with the present embodiment, namely the equal change done of all disclosed spirit or modification, still drop in the scope of the claims of the present invention.
Claims (5)
1. a preparation method for the all-solid-state battery of skeletal support alloy anode, is characterized in that, comprises the following steps:
(1) preparation of skeletal support alloy anode: alloy material of cathode adopts Li-B alloy sheet, solid electrolyte adopts Li-La-Zr-O solid electrolyte powder, Li-B alloy electrode plate surface passivation layer film is polished off, be the Li-La-Zr-O solid electrolyte powder of 30-300 micron by particle diameter, according to 0.1-1.5mg/cm
2uniform application is on Li-B alloy electrode plate surface, and powder covers on it by the pressure then applying 5-15MPa, obtains the skeletal support alloy material of cathode of electrolyte treatment;
(2) preparation of composite electrolyte: the molecular weight of the organic principle employing of composite electrolyte is polyethylene glycol polymer PEO or the plastic crystal type organic succinonitrile SN of 6000-50 ten thousand, solvent is tetrahydrofuran THF, and electrolyte is two (trimethyl fluoride sulfonyl) imine lithium LiTFSI; The inorganic constituents of composite electrolyte is that particle size is less than 300 object Li-Al-Ge-P powder or Li-Al-Ti-P powder; Preparation method is as follows:
Be (4-16) in EO segment and Li ion according to mol ratio: 1 ratio takes PEO and LiTFSI, adds THF and is dissolved, 30-90 DEG C of stirring under inert atmosphere, and by mass percentage, solid content is the solution of 1-10% in configuration; According to mass ratio (PEO+LiTFSI): Li-Al-Ge (Ti)-P powder=1:(3-49), add Li-Al-Ge (Ti)-P powder, by its mixing and stirring, obtain the slurry of composite solid electrolyte; Or
SN is dissolved at the temperature of 50 DEG C, then adds LiTFSI, be mixed with the solution of 0.2-1.0mol/L; According to mass ratio (SN+LiTFSI): Li-Al-Ge (Ti)-P powder=1:(3-49), add Li-Al-Ge (Ti)-P powder, by its mixing and stirring, obtain the mixture of composite solid electrolyte;
(3) assembling of all-solid-state battery: the Li-B alloy electrode plate surface of the process that the slurry uniform application of composite solid electrolyte step (2) prepared obtains in step (1), then to spend the night at 50-100 DEG C oven dry, by the Li-B alloy electrode plate being coated with composite electrolyte of oven dry under the pressure of 5-20MPa, composite electrolyte is covered smooth, cover on composite electrolyte by the anode electrode sheet processed, assembling obtains all-solid-state battery.
2. the preparation method of the all-solid-state battery of skeletal support alloy anode according to claim 1, is characterized in that, in described step (1), the particle diameter of Li-La-Zr-O solid electrolyte powder is 100 microns, according to 0.5mg/cm
2all with spread upon Li-B alloy electrode plate surface, powder covers on it by the pressure then applying 10MPa.
3. the preparation method of the all-solid-state battery of skeletal support alloy anode according to claim 1, is characterized in that, in described step (2), the molecular weight of PEO is 100,000; EO segment and Li ion are 8:1 according to molal weight ratio; According to mass ratio (PEO+LiTFSI): Li-Al-Ge (Ti)-P powder=1:19.
4. the preparation method of the all-solid-state battery of skeletal support alloy anode according to claim 1, is characterized in that, in described step (3), the process of anode electrode sheet: positive pole consist of active substance ferrous lithium phosphate LiFePO
4, binding agent Kynoar PVDF, conductive agent SP; Anode portion ionic conduction composition is polyethylene glycol polymer PE0, and the solvent dissolving PEO is THF, and electrolyte is LiTFSI; By active material LiFePO
4, the ratio of binding agent PVDF and conductive agent SP 8:1:1 in mass ratio applies into electrode, and after drying, cut-parts are for subsequent use; The PEO/LiTFSI solution that step (2) prepares is added drop-wise to anode electrode sheet surface, forms thin layer PEO/LiTFSI layer, oven dry of then it being spent the night at the temperature of 70 DEG C.
5. the all-solid-state battery of skeletal support alloy anode prepared by the preparation method as described in any one of claim 1-4.
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| 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 |
| CN106207086B (en) * | 2016-08-15 | 2019-06-28 | 无锡海特新材料研究院有限公司 | High capacity solid lithium ion battery negative electrode material and battery cathode and preparation method thereof |
| CN106207086A (en) * | 2016-08-15 | 2016-12-07 | 无锡海特新材料研究院有限公司 | High power capacity solid lithium ion battery negative material and battery cathode and preparation method thereof |
| CN106784636A (en) * | 2016-12-29 | 2017-05-31 | 中国电子科技集团公司第十八研究所 | Method for treating surface of metal lithium by using iodine solution and application of method in solid-state battery |
| CN108376763A (en) * | 2018-02-05 | 2018-08-07 | 电子科技大学 | A kind of composite negative pole structure, solid lithium battery battery core, solid lithium battery and preparation method thereof |
| CN109167080A (en) * | 2018-09-12 | 2019-01-08 | 哈尔滨工业大学（威海） | A kind of high voltage lithium thermal cell |
| CN109546079B (en) * | 2018-11-23 | 2022-05-17 | 哈尔滨工业大学 | High-voltage composite solid positive electrode and preparation method thereof, and all-solid-state battery comprising positive electrode and preparation method thereof |
| CN109546079A (en) * | 2018-11-23 | 2019-03-29 | 哈尔滨工业大学 | A kind of high voltage type composite solid anode and preparation method thereof and the all-solid-state battery comprising the anode and preparation method thereof |
| CN110534803A (en) * | 2019-09-17 | 2019-12-03 | 广东天劲新能源科技股份有限公司 | A kind of preparation method for the solid polyelectrolyte introducing halide lithium salts |
| CN111786025A (en) * | 2020-06-22 | 2020-10-16 | 安徽迅启电源科技有限公司 | All-solid-state lithium battery and preparation method thereof |
| CN111786025B (en) * | 2020-06-22 | 2022-07-12 | 安徽迅启新能源科技有限公司 | All-solid-state lithium battery and preparation method thereof |
| CN112563456A (en) * | 2020-12-07 | 2021-03-26 | 上海电力大学 | Modified lithium metal negative electrode, preparation method thereof and button cell |
| CN113488644A (en) * | 2021-06-25 | 2021-10-08 | 万向一二三股份公司 | Preparation method of high-nickel ternary material and application of high-nickel ternary material in solid-state lithium ion battery positive plate |
| CN114141980A (en) * | 2021-11-24 | 2022-03-04 | 蜂巢能源科技(无锡)有限公司 | Solid-state lithium-sulfur battery anode and all-solid-state lithium-sulfur battery |
| CN116005055A (en) * | 2022-12-12 | 2023-04-25 | 北京有色金属与稀土应用研究所有限公司 | Thermal battery anode lithium boron material and preparation method thereof |
| CN116005055B (en) * | 2022-12-12 | 2024-04-30 | 北京有色金属与稀土应用研究所有限公司 | Thermal battery anode lithium boron material and preparation method thereof |
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