CN108461715A - A kind of preparation method of solid state battery cathode of lithium - Google Patents
A kind of preparation method of solid state battery cathode of lithium Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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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- 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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Abstract
The present invention relates to a kind of preparation method of solid state battery cathode of lithium, the preparation method includes：（1）Lithium salts, organic solvent, electrolysis additive are configured to electrolyte; the molar concentration of lithium salts in organic solvent is 1 mol/L; then lithium metal is put into electrochemistry in electrolyte for 1.0% and recycled in advance by the mass concentration of electrolysis additive, layer protecting film is formed on lithium anode surface；（2）By step in glove box（1）Lithium anode is cleaned with electrolyte solvent after middle cycle, wait for solvent volatilization totally to get；Compared with prior art, preparation method of the invention is simple to operation, is easy to regulate and control；Simultaneously, the solid state battery of the cathode of lithium assembling prepared using the method for the present invention not only avoids the adverse reaction between cathode of lithium and solid electrolyte interface well, but also there is excellent cycle performance and low-down impedance, show good chemical property.
Description
Technical field
The invention belongs to solid state cell technology field more particularly to a kind of preparation methods of solid state battery cathode of lithium.
Background technology
In recent years, with the rapid development of electric vehicle and high-end portable formula electronic equipment, to high energy density cells
Demand is more and more urgent.Lithium metal is up to 3860mAhg-1Superelevation specific capacity and minimum electrochemical potential (relative standard hydrogen electricity
Extremely -3.04V) become the ultimate cathode of high-energy density lithium battery.In addition, at this stage with lithium-sulfur cell and lithium air electricity
The lithium metal battery that Chi Wei is represented is considered as most promising next-generation energy storage system.However, lithium metal is being circulated throughout
It will produce Li dendrite in journey, therefore reduce cycle coulombic efficiency and the service life of metal lithium electrode.More seriously, dendrite is continuous
Growth can further cause safety problem (such as on fire, explosion etc.), these factors all strongly limit the quotient of lithium anode
Industry application.
The fast development of solid state ionic conductor material in recent years accelerates the process of lithium anode large-scale application, but
It is that, due to chemistry or electrochemical incompatibility between most inorganic solid electrolyte and lithium anode, deteriorated significantly lithium
The interface performance of cathode/solid electrolyte, therefore, no dendrite generate and with stable metal lithium of the electrolyte without bad interfacial reaction
Cathode plays key effect to the long-term cycle stability of lithium metal solid state battery.
To improve the interface compatibility of lithium anode/solid electrolyte, the generation of Li dendrite, scientists being inhibited to propose
A variety of solutions.Jadhav research teams are using RF- sputtering methods in Li1.5Al0.5Ge1.5(PO)4(LAGP) surface introduces
The unformed films of LIPON are contacted with completely cutting off lithium metal with LAGP, to mitigate the adverse reaction between interface, the Li-O2 being assembled into
Battery has good cyclical stability (Journal of Power Sources under the restriction capacity of 1000mA h g-1
2017,340,294-301).One layer of Al modifies using atomic layer deposition method in metallic lithium surface in Hu research teams2O3, then change
For Li-Al-O electrode layers, it is steady that the lithium metal by modification remains good interface during subsequent circulating battery
Qualitative and excellent chemical property (DOI:10.1038/nmat4821).Although these methods are to improve cathode of lithium/solid-state electricity
Solution matter interface stability performance provides method, but complicated film preparing system use and high cost limit these methods
Practical application, some even need to be handled at high temperature, instead to the Li at interface+Transmission characteristic causes adverse effect.
In addition, the protection composition of layer and structure that are prepared by these methods are single, it cannot fully meet in solid state battery and protective layer is carried
The requirements such as the high ionic conductivity that goes out, low conductivity, mechanical property be good.Xu team is by cladding process in cathode of lithium and solid state electrolysis
Matter interface introduces PEO base composite solid electrolytes, although improving interface compatibility, composite solid electrolyte is relatively low at room temperature
Lithium ion conductivity limit the promotion (J.Mater.Chem.A, 2017,5,16984) of solid state battery high rate performance.
To sum up, the existing method for solving the problems, such as solid electrolyte/cathode of lithium interface compatibility still has processing step
It is complicated, of high cost, obtain interface performance it is bad the problems such as, therefore, it is necessary to study simple and practicable method solve solid-state electricity
Matter/cathode of lithium interface compatibility problem is solved, this has huge meaning to the long-term cycle stability of lithium metal solid state battery.
Invention content
For the above-mentioned prior art the problem of, the purpose of the present invention is to provide a kind of solid state battery cathode of lithium
Preparation method, compared with prior art, preparation method of the invention is simple to operation, is easy to regulate and control；Meanwhile utilizing the present invention's
The solid state battery of cathode of lithium assembling prepared by method not only avoids between cathode of lithium and solid electrolyte interface not well
Good reaction, but also there is excellent cycle performance and low-down impedance, show good chemical property.
An object of the present invention is to provide a kind of preparation method of solid state battery cathode of lithium.
The second object of the present invention is to provide the solid state battery for the solid state battery cathode of lithium for utilizing the method for the present invention to prepare.
The third object of the present invention is to provide the preparation method of above-mentioned solid state battery cathode of lithium and the application of solid state battery.
For achieving the above object, the invention discloses following technical proposals：
First, the invention discloses a kind of preparation method of solid state battery cathode of lithium, the preparation method includes：
(1) lithium salts, organic solvent, electrolysis additive are configured to electrolyte, lithium salts in organic solvent mole dense
Degree is 1mol/L, then lithium metal is put into electrochemistry in electrolyte for 1.0% and recycled in advance by the mass concentration of electrolysis additive,
Layer protecting film is formed on lithium anode surface；
(2) in glove box will lithium anode is cleaned with electrolyte solvent after cycle in step (1), after wait for that solvent volatilizees
Totally to get.
The lithium salts includes：Double fluorine sulfimide lithiums, bis- (trimethyl fluoride sulfonyl) imine lithiums, lithium hexafluoro phosphate, hexafluoro boron
One or more of sour lithium, lithium perchlorate, hexafluoroarsenate lithium, biethyl diacid lithium borate, difluorine oxalic acid boracic acid lithium.
The organic solvent includes：Tetrahydrofuran, dimethyl sulfoxide (DMSO), ethylene carbonate, dimethyl carbonate, 1,3- dioxies
Pentane, one in glycol dimethyl ether, propene carbonate, diethyl carbonate, sulfolane, the first and second base carbonic esters, ethyl acetate
Kind is several.
The additive includes fluorinated ethylene carbonate, lithium nitrate, lithium iodide, lithium fluoride, more lithium sulfides, lithium carbonate, carbon
Sour vinylene, sulfur dioxide, ethylene sulfite, lithium chloride, propylene sulfite, nitrogen dioxide, carbon dioxide, water, two
One or more of methyl sulfite, lithium sulfide, lithium sulfite, lithium sulfate, lithium bromide, organo-silicon compound.
It is needed in glove box to lithium surface nylon before preparing solid state battery cathode of lithium using the pre- cycle of electrochemistry
Brush dips hexamethylene and is cleaned, to remove the impurity on surface.
It is 0.5mA/cm that the electrochemistry recycles the current density taken in advance2。
It is -1~1V that the electrochemistry recycles the limitation voltage range taken in advance.
The cycle-index that the electrochemistry recycles in advance is 1 circle.
Secondly, the invention discloses a kind of all-solid-state batteries, including lithium anode manufactured in the present embodiment, solid state electrolysis
Matter, positive electrode；The solid electrolyte is LAGP inorganic ceramics piece or LAGP-PEO composite solid electrolyte films；It is described just
Pole material is LiFePO4；Lithium anode, LAGP inorganic ceramics piece, iron phosphate lithium positive pole are stacked successively and are assembled into solid-state
Battery to get.
The LiFePO4 is prepared by following methods：It is 7 to weigh mass ratio:1:2 LiFePO4, super P and PEO
(LITFSI) it is scattered in tetrahydrofuran, after stirring 12h slurry even application is dried in vacuo 12h on aluminium foil at 80 DEG C, cut out
Piece to get.
Finally, the invention discloses the negative material of the preparation method of solid state battery cathode of lithium of the present invention and its preparation and
The application of all-solid-state battery, the application include in lithium battery, electric vehicle or energy-storage system.
Compared with prior art, the present invention achieves following advantageous effect：
(1) present invention forms one layer of ex situ on lithium anode surface by the pre- round-robin method of simple electrochemistry and consolidates
State electrolyte protective film, the component and structure of the protective layer can be by changing the electrolyte that use and electrochemistry recycles in advance
Parameter carries out Effective Regulation, and method is simple, be easy to industrialized production.
(2) protective film for being coated on cathode of lithium surface prepared by the present invention is high with ionic conductivity, electronic isolation rate is high,
The characteristics of good mechanical property, will not interfere the migration of lithium ion during all-solid-state battery charge and discharge cycles, to improving solid-state electricity
The high rate performance in pond plays an important role.
(3) present invention only need to increase the pre- cyclic process of electrochemistry in all-solid-state battery negative material preparation process, operate
Simply, the production of the existing interface side reaction between solid electrolyte when all-solid-state battery uses lithium metal as cathode is solved
It is raw so that lithium anode can be used directly in solid state battery, give full play to the specific capacity advantage of lithium anode.
(4) utilize lithium anode assembling prepared by the method for the present invention solid state battery is not only safe and stable, coulombic efficiency
Height, lithium metal/solid electrolyte interface compatibility are good, and manufacturing cost is low, is easy to regulate and control, and are suitable for commercial application.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is the XPS spectrum figure of lithium anode surface protection film prepared by the embodiment of the present invention 1.
Fig. 2 is SEM of the lithium anode of the preparation of the embodiment of the present invention 1 under different current densities after the pre- cycle of electrochemistry
Figure；Wherein, (a) initial lithium piece, (b) 0.1mA cm-2、(c)0.5mA cm-2、(d)1.0mA cm-2。
Fig. 3 is the cycle performance figure of the all-solid-state battery and comparison solid state battery of the embodiment of the present invention 1.
Fig. 4 is cyclical voltage-time graph of the all-solid-state battery and comparison solid state battery of the embodiment of the present invention 1.
The all-solid-state battery and the lithium electrode surface pattern after comparison solid state battery cycle that Fig. 5 is the embodiment of the present invention 2
SEM schemes.
Fig. 6 is the cycle performance figure of the all-solid-state battery and comparison solid state battery of the embodiment of the present invention 2.
Fig. 7 is the impedance that 2 all-solid-state battery of the embodiment of the present invention and comparison solid state battery store different time at 50 DEG C
Variation.
Fig. 8 be comparison all-solid-state battery occurs on surface after cycling in the embodiment of the present invention 2 Li dendrite in the secure execution mode (sem
Shape appearance figure.
Fig. 9 is cyclical voltage-time graph of the all-solid-state battery and comparison solid state battery of the embodiment of the present invention 2；Wherein,
(c) it is the enlarged drawing of dotted portion (d).
In above-mentioned Fig. 3-7,9, (a) and (b) respectively represent the comparison solid state battery of corresponding embodiment assembling and complete solid
State battery.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As described in background, the existing method for solving the problems, such as solid electrolyte/cathode of lithium interface compatibility is still
The problems such as interface performance that there are processing steps is complicated, of high cost, obtains is bad, therefore, the present invention propose a kind of solid-state electricity
The preparation method of pond cathode of lithium, in conjunction with the drawings and specific embodiments, the present invention is described further.
Embodiment 1
1, a kind of preparation method of solid state battery cathode of lithium, includes the following steps：
(1) LiTFSI for being configured to be divided into 1mol/L first is dissolved in DOL/DME/FEC (volume ratios 9:9:2) in, then add
It is 1.0% LiNO to add mass concentration3Electrolyte；
(2) lithium anode is put into the electrolyte of step (1), assembling Li/Li Symmetrical cells, after battery standing 12h
It carries out electrochemistry to recycle in advance, the parameter that electrochemistry recycles in advance is：Current density is 0.5mA/cm2；Limit voltage range be -1~
1V；Cycle-index is 1 circle.
(3) battery after cycle in step (2) is dismantled in glove box, takes out lithium anode, uses electrolyte solvent
Carefully cleaned, be subsequently placed in glove box wait for solvent volatilization totally to get.
2, a kind of all-solid-state battery, including lithium anode manufactured in the present embodiment, solid electrolyte, positive electrode；Institute
It is LAGP inorganic ceramic pieces to state solid electrolyte；The positive electrode is LiFePO4.
The LiFePO4 is prepared by following methods：It is 7 to weigh mass ratio:1:2 LiFePO4, super P and PEO
(LITFSI) it is scattered in tetrahydrofuran, after stirring 12h slurry even application is dried in vacuo 12h on aluminium foil at 80 DEG C, cut out
Piece to get.
Above-mentioned lithium anode, LAGP inorganic ceramics piece, iron phosphate lithium positive pole are stacked successively and are assembled into power solid-state electricity
Chemical property is tested in pond.
3, all-solid-state battery is compared, includes lithium anode, solid electrolyte, positive electrode without any processing；Institute
It is LAGP inorganic ceramic pieces to state solid electrolyte；The positive electrode is LiFePO4.
The LiFePO4 is identical as preparation method in all-solid-state battery.
Above-mentioned lithium anode, LAGP inorganic ceramics piece, iron phosphate lithium positive pole are stacked successively and solid-state in contrast with assembling
Battery tests chemical property.
Performance test：
(1) XPS tests are carried out to lithium anode manufactured in the present embodiment, the results are shown in Figure 1, can from Fig. 1
Go out：It is circulated in advance by electrochemistry and contains abundant LiF and Li in the SEI films of metallic lithium surface generation3N, LiF have low Li
+ diffusion energy and high surface energy may advantageously facilitate the diffusion into the surface of Li+ and form the uniform surface protection film to compact, in addition
Electronic isolation characteristic (conductivity~10 of LiF-31S cm-1) effectively prevent transmission of the electronics in SEI films.Li3N is all
Solid electrolyte in contain higher ionic conductivity (6*10-3S cm-1), be conducive to the diffusion for accelerating Li+, therefore, this layer
Rich LiF＆Li3The SEI films of N can play a very good protection to lithium metal, and not influence the efficiency of transmission of Li+.
(2) by lithium anode manufactured in the present embodiment, electrochemistry is seen in the secure execution mode (sem after recycling in advance under different current densities
It examines, the results are shown in Figure 2, as can be seen from Figure 2：Compared to initial Li foils, the metal that SEI is protected after electrochemistry recycles
There is lithium surface topography evenly, the protrusion on surface or gully obviously to weaken, the surface topography of uniform ground be conducive to electronics/
Ion is uniformly distributed, and substantially reduces the metal caused by surface electronic/ion distribution is uneven caused by point effect
The nonuniform deposition of lithium can effectively inhibit the formation of Li dendrite.
(3) to the present embodiment assembling all-solid-state battery and comparison solid state battery under 50 DEG C and 0.1C of current density into
Row cycle performance is tested；It is to replace lithium metal manufactured in the present embodiment with the cathode of lithium without any processing to bear to compare solid state battery
After extremely, prepared with positive electrode (preparation method is identical) using identical solid electrolyte, test results are shown in figure 3；
As can be seen from Figure 3：Use all solid state electricity of LAGP bases of the cathode of lithium assembling manufactured in the present embodiment with SEI film protective layers
Pond has the cyclical stability significantly improved, and the battery assembled using untreated cathode of lithium is with the increasing for recycling the number of turns
Add, specific capacity drastically declines.
(4) all-solid-state battery to the present embodiment assembling and comparison solid state battery are in 50 DEG C and 0.05mA/cm2Electric current it is close
The lower test loop voltage-time curve of degree, as a result as shown in Figure 4；As can be seen from Figure 4：It is negative using untreated lithium
The serious polarization of all solid state LAGP bases Symmetrical cells of pole assembling, cycle just triggered voltage less than 20 hours and outrange protection,
This illustrates that electrode/electrolyte interface is extremely unstable, and pair that the cathode of lithium for using SEI films manufactured in the present embodiment to protect assembles
Battery polarization is claimed to be obviously reduced, cyclical stability greatly improves, and cycle life under this condition extends to 65h.
Embodiment 2
1, a kind of preparation method of solid state battery cathode of lithium, embodiment 1.
2, a kind of all-solid-state battery, with embodiment 1, difference lies in：The solid electrolyte is LAGP-PEO composite solids
Electrolytic thin-membrane.
3, all-solid-state battery is compared, with embodiment 1, difference lies in：The solid electrolyte is LAGP-PEO composite solids
Electrolytic thin-membrane.
Performance test：
(1) by lithium anode manufactured in the present embodiment in 0.1mA cm-2Electrochemistry assembles after recycling in advance under current density
Li-LAGP/PEO-LFP carries out observation surface topography in the secure execution mode (sem after recycling 160 circles at 0.1C, and the results are shown in Figure 5；From Fig. 5
In it can be seen that：Fig. 5 (a) is pattern after untreated cathode of lithium cycle, it can be seen that electrode surface is very uneven, has big
The dendron shape Li dendrite of amount generates, and (Fig. 5 b) uniform surface degree after the cathode of lithium cycle that SEI films made from the present embodiment are protected
It significantly improves, there is no Li dendrite generation after 160 circle of cycle.
(2) to the present embodiment assembling all-solid-state battery and comparison solid state battery under 50 DEG C and 0.1C of current density into
Row cycle performance is tested；Test results are shown in figure 6；As can be seen from Figure 6：It is protected using SEI films manufactured in the present embodiment
The Li-LAGP/PEO-LFP all-solid-state batteries of cathode of lithium assembling show excellent long-term cycle stability, after 200 circle of cycle
Capacity retention ratio is 96%, and the battery capacity assembled using untreated cathode of lithium is from 143.6mA h g-1160 circle of cycle
After drop sharply to 86mA h g-1, and coulombic efficiency is unstable in cyclic process, therefore illustrate that electrochemistry recycles preparation in advance
The cathode of lithium of SEI films protection substantially increases the stability at electrode/interface in cycle.
(3) it after the all-solid-state battery of the present embodiment and comparison all-solid-state battery being stored different time at 50 DEG C, measures
Impedance variations, the results are shown in Figure 7；As can be seen from Figure 7：The Symmetrical cells impedance storage of untreated cathode of lithium assembling
~1100 Ω are drastically increased to from~980 Ω after 72h, as time went on to 1800h, impedance continues to increase to~6700 Ω,
And the impedance of battery 1800h of the cathode of lithium assembling of SEI films protection only has 1700 Ω, this illustrate the cathode of lithium of SEI films protection with
Compatibility between electrolyte substantially improves.
(4) Li dendrite occurred on comparison all-solid-state battery in the present embodiment after cycling surface is seen in the secure execution mode (sem
It examines, the results are shown in Figure 8；As can be seen from Figure 8：In the Li-LAGP/PEO-LFP assembled using untreated cathode of lithium
Full battery has apparent Li dendrite to generate after cycling.
(5) all-solid-state battery to the present embodiment assembling and comparison solid state battery are in 50 DEG C and 0.05mA/cm2Electric current it is close
The lower test loop voltage-time curve of degree, as a result as shown in Figure 9；As can be seen from Figure 9：The lithium protected using SEI films is negative
The Li-LAGP/PEO-Li Symmetrical cells of pole assembling show the polarization being obviously reduced, long-term cycle stability in cyclic process
The Symmetrical cells for greatly improving, and being assembled using untreated cathode of lithium are sharply increased with the polarization that carries out of cycle, constantly
Increased polarization may be that the interface caused by the product for the low conductivity being continuously generated in electrode/electrolyte interface is continuous
Caused by increased impedance, and polarization continued to increase 70 hours after, there is unstable reforming phenomena in voltage curve, this
Caused by may be the inside battery micro-short circuit as caused by Li dendrite.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for those skilled in the art
For member, the application can have various modifications and variations.Any modification made by within the spirit and principles of this application,
Equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of preparation method of solid state battery cathode of lithium, it is characterised in that：The preparation method includes：
(1) lithium salts, organic solvent, electrolysis additive are configured to electrolyte, the molar concentration of lithium salts in organic solvent is
1mol/L, then lithium metal is put into electrochemistry in electrolyte for 1.0% and recycled in advance by the mass concentration of electrolysis additive, in gold
Belong to cathode of lithium surface and forms layer protecting film；
(2) lithium anode after cycle in step (1) is cleaned in glove box with electrolyte solvent, waits for that solvent volatilization is clean,
To obtain the final product.
2. the preparation method of solid state battery cathode of lithium as described in claim 1, it is characterised in that：The lithium salt solution includes：
Double fluorine sulfimide lithiums, bis- (trimethyl fluoride sulfonyl) imine lithiums, lithium hexafluoro phosphate, hexafluoro lithium borate, lithium perchlorate, hexafluoroarsenate
One or more of lithium, biethyl diacid lithium borate, difluorine oxalic acid boracic acid lithium.
3. the preparation method of solid state battery cathode of lithium as described in claim 1, it is characterised in that：The additive is fluoro carbon
Vinyl acetate, lithium nitrate, lithium iodide, lithium fluoride, more lithium sulfides, lithium carbonate, vinylene carbonate, sulfur dioxide, sulfurous acid second
Enester, lithium chloride, propylene sulfite, nitrogen dioxide, carbon dioxide, water, dimethyl sulfite, lithium sulfide, lithium sulfite,
One or more of lithium sulfate, lithium bromide, organo-silicon compound.
4. the preparation method of solid state battery cathode of lithium as described in claim 1, it is characterised in that：The organic solvent includes：
Tetrahydrofuran, dimethyl sulfoxide (DMSO), ethylene carbonate, dimethyl carbonate, 1,3- dioxolanes, glycol dimethyl ether, carbonic acid third
One or more of enester, diethyl carbonate, sulfolane, the first and second base carbonic esters, ethyl acetate.
5. such as the preparation method of claim 1 any one of them solid state battery cathode of lithium, it is characterised in that：The electrochemistry is pre-
It is -1~1V to recycle the limitation voltage range taken.
6. the preparation method of solid state battery cathode of lithium as described in claim 1, it is characterised in that：The electrochemistry in advance adopt by cycle
The current density taken is 0.5mA/cm2。
7. the preparation method of solid state battery cathode of lithium as described in claim 1, it is characterised in that：What the electrochemistry recycled in advance
Cycle-index is 1 circle.
8. a kind of all-solid-state battery includes lithium anode, solid state electrolysis as prepared by any one of claim 1-7 preparation method
Matter, positive electrode；Lithium anode, solid electrolyte, positive electrode are stacked successively and assembled to get.
9. all-solid-state battery as claimed in claim 8, it is characterised in that：The solid electrolyte be LAGP inorganic ceramics piece or
LAGP-PEO composite solid electrolyte films；The positive electrode is LiFePO4.
10. if the preparation of any one of claim 1-7 preparation methods and/or all-solid-state battery as claimed in claim 8 or 9 are in lithium
Application in battery, electric vehicle or energy storage material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810220067.4A CN108461715B (en) | 2018-03-16 | 2018-03-16 | Preparation method of solid-state battery lithium cathode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810220067.4A CN108461715B (en) | 2018-03-16 | 2018-03-16 | Preparation method of solid-state battery lithium cathode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108461715A true CN108461715A (en) | 2018-08-28 |
| CN108461715B CN108461715B (en) | 2021-10-26 |
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| CN109244544A (en) * | 2018-11-19 | 2019-01-18 | 哈尔滨工业大学 | The preparation method and applications of the magnesium sulphur battery electrolyte of the additive containing lithium ion |
| CN109273761A (en) * | 2018-09-17 | 2019-01-25 | 浙江大学 | A method of solid electrolyte interface film is prepared on lithium metal surface |
| CN109698396A (en) * | 2019-01-09 | 2019-04-30 | 山东大学 | A kind of lithium-air battery based on lithium alloy cathode |
| CN109698319A (en) * | 2018-12-28 | 2019-04-30 | 蜂巢能源科技有限公司 | Cathode of solid state battery and preparation method thereof and solid state electrode |
| CN109786675A (en) * | 2018-12-28 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Interface modification method for metal lithium cathode of solid-state lithium battery |
| CN109786692A (en) * | 2018-12-25 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Surface nitriding modification method of metal lithium electrode, obtained metal lithium cathode and application |
| CN110391409A (en) * | 2019-07-25 | 2019-10-29 | 昆山宝创新能源科技有限公司 | Lithium cell cathode material and preparation method thereof and lithium battery |
| CN110429325A (en) * | 2019-08-07 | 2019-11-08 | 宁德国泰华荣新材料有限公司 | It is a kind of can room temperature-operating solid state battery and preparation method thereof |
| CN110911685A (en) * | 2019-11-28 | 2020-03-24 | 宁德新能源科技有限公司 | Composition for negative electrode, and protective film, negative electrode and device comprising same |
| CN111799445A (en) * | 2020-08-24 | 2020-10-20 | 中南大学 | Lithium metal anode and preparation and application thereof |
| CN111816843A (en) * | 2020-06-30 | 2020-10-23 | 傲普(上海)新能源有限公司 | Solid-state battery and manufacturing method thereof |
| CN112072076A (en) * | 2020-07-22 | 2020-12-11 | 宁波大学 | Modification method for surface of negative electrode of lithium metal battery |
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| CN114868274A (en) * | 2019-12-20 | 2022-08-05 | 尤米科尔公司 | Solid electrolyte mesophase in lithium secondary batteries |
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| CN109273761A (en) * | 2018-09-17 | 2019-01-25 | 浙江大学 | A method of solid electrolyte interface film is prepared on lithium metal surface |
| CN109244544B (en) * | 2018-11-19 | 2020-05-19 | 哈尔滨工业大学 | Preparation method and application of magnesium-sulfur battery electrolyte containing lithium ion additive |
| CN109244544A (en) * | 2018-11-19 | 2019-01-18 | 哈尔滨工业大学 | The preparation method and applications of the magnesium sulphur battery electrolyte of the additive containing lithium ion |
| CN109786692A (en) * | 2018-12-25 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Surface nitriding modification method of metal lithium electrode, obtained metal lithium cathode and application |
| CN109698319A (en) * | 2018-12-28 | 2019-04-30 | 蜂巢能源科技有限公司 | Cathode of solid state battery and preparation method thereof and solid state electrode |
| CN109786675A (en) * | 2018-12-28 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Interface modification method for metal lithium cathode of solid-state lithium battery |
| CN109698396A (en) * | 2019-01-09 | 2019-04-30 | 山东大学 | A kind of lithium-air battery based on lithium alloy cathode |
| CN113767488A (en) * | 2019-05-02 | 2021-12-07 | 美敦力公司 | Electrolyte additives in primary batteries for medical devices |
| CN110391409A (en) * | 2019-07-25 | 2019-10-29 | 昆山宝创新能源科技有限公司 | Lithium cell cathode material and preparation method thereof and lithium battery |
| CN110429325A (en) * | 2019-08-07 | 2019-11-08 | 宁德国泰华荣新材料有限公司 | It is a kind of can room temperature-operating solid state battery and preparation method thereof |
| CN110911685A (en) * | 2019-11-28 | 2020-03-24 | 宁德新能源科技有限公司 | Composition for negative electrode, and protective film, negative electrode and device comprising same |
| WO2021103523A1 (en) * | 2019-11-28 | 2021-06-03 | Ningde Amperex Technology Limited | Composition for anode, and protective film, anode, and device comprising same |
| CN114868274B (en) * | 2019-12-20 | 2024-01-16 | 尤米科尔公司 | Solid electrolyte mesophase in lithium secondary batteries |
| CN114868274A (en) * | 2019-12-20 | 2022-08-05 | 尤米科尔公司 | Solid electrolyte mesophase in lithium secondary batteries |
| CN111816843A (en) * | 2020-06-30 | 2020-10-23 | 傲普(上海)新能源有限公司 | Solid-state battery and manufacturing method thereof |
| CN112072076B (en) * | 2020-07-22 | 2021-07-27 | 宁波大学 | Modification method for surface of negative electrode of lithium metal battery |
| CN112072076A (en) * | 2020-07-22 | 2020-12-11 | 宁波大学 | Modification method for surface of negative electrode of lithium metal battery |
| CN111799445A (en) * | 2020-08-24 | 2020-10-20 | 中南大学 | Lithium metal anode and preparation and application thereof |
| CN112490411A (en) * | 2020-11-25 | 2021-03-12 | 哈尔滨工业大学 | Method for protecting lithium metal negative electrode through in-situ film forming |
| CN112490411B (en) * | 2020-11-25 | 2022-04-12 | 哈尔滨工业大学 | Method for protecting lithium metal negative electrode through in-situ film forming |
| CN113764822A (en) * | 2021-09-09 | 2021-12-07 | 武汉科技大学 | High-ionic-conductivity composite coating film for lithium primary battery and preparation method thereof |
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