CN110233285A - A method of improving solid state battery interface stability using polymer dielectric - Google Patents
A method of improving solid state battery interface stability using polymer dielectric Download PDFInfo
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Abstract
A method of improving solid state battery interface stability using polymer dielectric, belongs to solid state battery technical field.Using the classifying porous polymer dielectric film of preparation as cushioning layer material, it is placed between electrode material and the solid electrolyte, good contact is formed with positive electrode, electrolyte and lithium metal, interface impedance is effectively reduced, and the direct haptoreaction of solid electrolyte and lithium metal can be slowed down, all-solid-state battery has preferable cyclical stability.
Description
Technical field
The present invention relates to a kind of phosphoric acid germanium lithiums of metallic aluminium doping, and apply the material and gel polymer electrolyte
The lithium ion battery technology that PVDF-HFP is combined.Phosphoric acid germanium lithium using aluminium doping is solid electrolyte, with above-mentioned preparation
Polymer dielectric constructs that lithium is all solid state or quasi- solid ionic battery as buffer layer, belongs to solid state battery technical field.
Background technique
It steps into 21 century, human society is just grown rapidly at an unprecedented rate, and the mankind are many in enjoyment advanced civilization
Also have to increasingly depleted in face of such as fossil fuel resource while benefit, Global Greenhouse Effect becomes clear day by day generated energy
Source environmental crisis, this also forces the mankind that must thoroughly change energy consumption patterns, greatly develops renewable and clean energy resource.It is same with this
When, the high-efficiency energy-storage device --- lithium ion battery --- as the important ring of clean energy resource has attracted extensive attention.At present
Most of lithium ion batteries are to carry out Li based on organic bath+Conduction, and then realize the storage and conversion of energy.That
, lithium ion battery still will receive the poor electrochemistry of its liquid organic electrolyte and thermostabilization in actual application
Property limitation, safety problem is also especially prominent, is easy to happen volatilization, leakage, induces fire, the safety accidents such as explosion.
In recent years, lithium an- ode is due to its high quality specific capacity (3860mAh g-1) and lower electrochemical potential
(to standard hydrogen electrode -3.04V) is considered the key component of next-generation high energy density cells.If using lithium metal as cathode
When, the continued propagation of Li dendrite will pierce through diaphragm, and battery plus-negative plate is caused to contact and internal short-circuit.And use solid electrolyte
Solid state battery device, higher mechanical strength can effectively inhibit Li dendrite bring short circuit problem.In addition, solid state electrolysis
There are also following advantages for matter, including (i) are not in liquid electrolyte leakage and flammability issues in solid state battery；(ii) have
The electrochemical window that can be expanded has the potentially possible of exploitation high-energy density solid state battery.Therefore, solid lithium ion is developed
Battery (SSLIBs) technology is with important application prospects, it is sufficient to the revolutionary variation for causing energy storage device and application, to concerning
The strategy such as national security also has very important effect.According to the electrolyte used, solid state battery can be mainly divided into inorganic solid
State electrolytic cell and polymer battery etc..However at present exploitation the superior solid state battery of performance, still suffer from it is many science with
Technological challenge: for example, the low-load of electrode material volume change, large interface (electrode/electrolyte) resistance, electrode active material,
Cyclical stability difference and security performance are low etc..However among great number of issues, how a major issue of urgent need to resolve is
Electrode and solid electrolyte interface compatibility are improved, can overcome the key of these problems is that introduce lithium be stablized and can be pressed down
Li dendrite processed has the middle layer of ionic conductance again.
The present invention is based on the fast-ionic conductor of preparation (NASICON) type solid electrolyte, dexterously constructed positive and negative anodes with
The buffer layer of solid electrolyte contact, effective solution solid-solid interface contact, and lithium metal can be inhibited to high price in electrolyte
The reduction of state ion.To realize the high conductance and solid secondary batteries stable operation of solid solid interface.
Summary of the invention
The purpose of the present invention is preparations to have high chemical stability, thermal stability, wide electrochemical window, good air-stable
Property and macroion conductance NASICON type solid electrolyte and prepare gel polymer electrolyte flexible as interface buffer
Layer, improve solid electrolyte and it is positive and with lithium an- ode solid-solid interface compatibility issue.Meanwhile the invention further relates to
Solid lithium ion battery containing this NASICON type oxide and padded coaming.
A kind of solid electrolyte LAGP powder, preparation NASICON structural chemistry general formula are LiN2(PO4)3, pass through element M portion
Divide or conductivity is improved in the position of replacing whole N, general formula is Li1+xMxN2-x(PO4)3。
Wherein M is the metallic element of relatively low valence state, can be Al, Cr, Ga, Fe, Sc, In, Lu, the elements such as Y, La
It is one or more；Preferably Al；
N can be the one or more of the elements such as Ti, Ge or V with the metal of relatively high valence state；Due to Ti4+It compares
Ge4+It is more easily restored by lithium metal, it is advantageous to be Ge；Further solid electrolyte is Li1+xAlxGe2-x(PO4)3；
Preferably；0 x≤2.5 <, most preferably x=0.5；
The preparation of solid electrolyte LAGP powder weighs lithium source, the source M, the source N and phosphate according to chemistry mole metering ratio,
It is dissolved in solvent A, solvent A can be deionized water etc., but not limited to this, after dispersing and dissolving is uniform, by pH tune in mixing liquid
It is not less than 12 to strong basicity, that is, pH, heats solvent evaporated after complete reaction, be completely dried to obtain crystalline solid, be fully ground postposition
In porcelain boat, moisture is set further to volatilize at a certain temperature, it is therefore preferable to 200~300 DEG C, after the completion of moisture evaporation, in height
Phosphorus source is decomposed under temperature, it is therefore preferable to 300 DEG C~400 DEG C, after obtained powder is repeatedly ground, at higher temperature lower preferably 800
Calcining is carried out at~900 DEG C can be obtained NASICON type LAGP powder.
Preferably, the source Li, for example, a hydronium(ion) lithia, anhydrous nitric acid lithium, lithium carbonate, lithium acetate or oxalic acid
Lithium；
Preferably, the source M can be oxide, hydroxide, chlorate, nitrate etc., for example, aluminium hydroxide, nine
Water aluminum nitrate, aluminium chloride, aluminium oxide etc.；
Preferably, the source N, for example, germanium dioxide, tetraethoxy germanium, tetramethoxy germanium；
Preferably, the source P, for example, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The temperature that the prior art generates NASICON type LAGP using melt pulling method is compared generally at 1200~1300 DEG C
Under the present invention reaction temperature can be significantly reduced using aqua-solution method；It needs to make when the prior art is prepared using sol-gal process
With raw material with high costs, such as tetraethoxy germanium or tetramethoxy germanium, the present invention is used using aqua-solution method in contrast
Reaction cost can be significantly reduced in germanium dioxide.
The electrolyte (such as Garnet-type electrolyte LLZO) of the prior art is unstable in air, to CO2And water sensitive,
The application of solid state battery is limited, the present invention overcomes the problems of the prior art, using the NASICON of preparation as solid state electrolysis
Matter has the following characteristics that
1. relatively low and simple and easy to control sintering temperature (being lower than 950 DEG C), avoids a large amount of lithium from losing；
2. being stabilized in air, to CO2And water and insensitive, it is also very stable to soda acid；
3. still NASICON type solid electrolyte, inadequate to lithium metal stability, positive tetravalence Ge may be reduced by lithium
Lower valency forms hybrid ionic electronic conductor.So in solid state battery, it is necessary to certain measure be taken to overcome above-mentioned ask
Topic provides a kind of modified membrane and separates electrolyte and lithium metal, but do not have to influence performance.
Further, the present invention also provides a kind of preparations of classifying porous polymer dielectric film, make the film table of preparation
The hole in face is relatively large, and more inward hole is smaller；The polymer electrolyte can be Kynoar, polyoxyethylene
Alkene, polyacrylonitrile, Kynoar are total to the polymer such as hexafluoropropene, but not limited to this, preferably Kynoar is total to hexafluoropropene,
Specifically includes the following steps: polymer electrolyte is dissolved in solvent B by a certain percentage, solvent B such as acetone or N, N-
Dimethylformamide, concentration are between 98%~99%；Such as 50~60 DEG C of stirrings are sufficiently uniformly dissolved it at a certain temperature,
To mixing liquid add a certain amount of non-solvent phase stirring at normal temperature (non-solvent phase and solvent phase volume ratio 1:10 to 1:15 it
Between), mutually for example deionized water or dehydrated alcohol is prepared on die substrate non-solvent after liquid to be mixed stirs evenly completely
Film is first placed in room temperature slow evaporation solvent, is subsequently placed in 50~60 DEG C of vacuum oven vacuum drying until solvent is waved completely
It distributes and classifying porous polymer dielectric film can be obtained.Electrolyte film thickness is preferably to be close to mold base between 50 to 100 μm
The one side of plate is the face A, and the one side in exposure air is the face B, then the face B surface is porous structure, and more inward hole is smaller.
A method of improving solid state battery interface stability using polymer dielectric and improve solid state battery performance,
It is characterized in that, using the classifying porous polymer dielectric film of preparation as cushioning layer material, is placed in electrode material and described
Between solid electrolyte, with positive electrode, electrolyte and lithium metal formed it is good contact, interface impedance is effectively reduced,
And the direct haptoreaction of solid electrolyte and lithium metal can be slowed down；Specifically include following methods:
(1) electrode prepares
The common positive and negative anodes collector of field of batteries is taken, by electrode material, binder and conductive additive with required matter
Amount is dissolved in solvent than uniformly mixing, is fully ground after mixing, gained slurry is applied on a current collector, is completely dried；It is viscous
The preferably common Kynoar (PVDF) of agent is tied, conductive additive preferably uses carbon black, acetylene black or graphite etc., but is not limited to
State material.
(2) gel polymer electrolyte middle layer
It classifying porous polymer dielectric film is cut into disk immerses in electrolyte and fully absorb, and by extra electrolysis
Liquid is dried with waterleaf paper；
(3) solid electrolyte potsherd
Solid electrolyte LAGP powder obtained is pressed into tabletting, at high temperature, such as 850~950 DEG C of calcinings 10~
12h, and with different meshes sand paper sanding and polishing.
(4) solid state battery is constructed
Take the pole piece of step (1) as the anode in solid state battery, using negative electrode materials such as lithium metals as cathode, step
(3) potsherd is as electrolyte, and thin polymer film is as the modifying interface between anode and electrolyte ceramics piece in step (2)
Layer；Electrolytic thin-membrane doubling (makes hole side inwardly, i.e., by classifying porous polymer dielectric film doubling, so that B in step (2)
Face and the face B are close to, and the structure of ABBA is formed) as the interface-modifying layer between cathode of lithium and potsherd, and it is encapsulated in button electricity
In the shell of pond, pressurization to get arrive solid state battery sample.
The present invention provides with high air stability, macroion conductance, wide electrochemical window solid lithium ion battery.
The present invention solves the problems, such as solid electrolyte and the point-to-point physical contact of electrode material solid solid interface, improves solid solid interface
Compatibility；Classifying porous polymeric membrane forms continuous lithium ion diffusion admittance in polymeric inner, is conducive to the expansion of lithium ion
It dissipates, while overcoming NASICON solid electrolyte, it is inadequate to lithium metal stability, form the deficiency of hybrid ionic electronic conductor；
And the thickness of classifying porous polymer film is similar to diaphragm, the face A contacted with cathode of lithium is conducive to inhibit lithium with respect to the structure of less porous
The growth of dendrite.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of NASICON type solid electrolyte LAGP；
Fig. 2 is pattern of the NASICON type solid electrolyte LAGP under field emission scanning electron microscope；
Fig. 3 is the ac impedance spectroscopy of NASICON type solid electrolyte LAGP；
Fig. 4 is pattern of the polymer dielectric film under field emission scanning electron microscope；
Fig. 5 is the schematic diagram for assembling all solid state lithium ion secondary cell；
Fig. 6 is that the LAGP potsherd of increase decorative layer does removing to Li and plating is tested；
Fig. 7 is the cyclic curve of all-solid-state battery.Figure (a) is that all-solid-state battery charge and discharge in first five week under 0.1C multiplying power are bent
Line；Figure (b) (c) is all-solid-state battery preceding 13 circle charging and discharging curve and long circulating performance map under 0.3C multiplying power respectively.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
According to the characteristic of aqua-solution method, it is preferable to use a hydronium(ion) lithia, aluminium hydroxide, germanium dioxide, biphosphate
Ammonium is as the raw material for preparing LAGP.According to Li1.5Al0.5Ge1.5(PO4)3Chemistry mole metering is than weighing a hydronium(ion) lithia (mistake
Amount 5% to 15%), aluminium hydroxide, germanium dioxide, ammonium dihydrogen phosphate (excessive 2%), it is soluble in water and use magnetic stirrer
Uniformly.After being uniformly dispersed, a certain amount of 28% weak aqua ammonia is added dropwise into mixing liquid and adjusts PH to strong basicity (12 or more), to anti-
Sand-bath heats solvent evaporated after answering completely, is completely dried to obtain crystalline solid.As solvent evaporates, white crystals thing is obtained.Sufficiently
Grinding obtains white powder, is placed in aluminium oxide porcelain boat, so that moisture is further volatilized in the dry 6h of air dry oven.In this stage
Drying temperature be higher than water boiling point, drying temperature is preferably 200 DEG C.After the completion of moisture evaporation, at 300 DEG C of heat preservation 6h, make
Phosphorus source is decomposed, and light yellowish brown powder is obtained；It is ground again, white can be obtained in 800 DEG C of heat preservation 8h in Muffle furnace
LAGP powder.Fig. 1 gives the X ray diffracting spectrum of LAGP, it was demonstrated that generates pure NASICON phase.
Embodiment 2
Solid electrolyte material is observed under a scanning electron microscope and shows pattern and particle diameter distribution.What Fig. 2 gave
Experimental result shows that particle size distribution is uniform, more tiny and more evenly compared to solid phase method particle.
Embodiment 3
The conductivity test of inorganic solid electrolyte passes through sputtering at potsherd both ends generally to block battery forms progress
Or evaporation metal, if Au or Ag is tested in this, as blocking electrode, since Au is to Li+With certain blocking action, because
Apparent capacitive reactance arc is presented in the low frequency range of impedance spectrum in this.The potsherd prepared is polished using different sand paper,
After LAGP potsherd surface gold-plating, ac impedance measurement has been carried out to LAGP potsherd.It is surveyed using EIS ac impedance spectroscopy
Examination.Frequency range is 10Hz~1MHz, and test temperature is room temperature.Fig. 3 is the ac impedance spectroscopy of LAGP potsherd, according to formula(d: potsherd thickness, cm；R: the total impedance of potsherd, Ω；S: the cross-sectional area of potsherd, cm-2) its room can be calculated
The lower ionic conductance of temperature is 1.11 × 10-4S.cm-1, substantially meet the conductivity demand of solid state battery.
Embodiment 4
0.5g Kynoar hexafluoropropene is total to by a certain percentage to be dissolved in acetone 12ml.In 50 DEG C of magnetic agitation feelings
Under condition, it is sufficiently uniformly dissolved it.1ml dehydrated alcohol is added to mixing liquid and in stirring at normal temperature.Liquid to be mixed stirs completely
After mixing uniformly, mixed liquor is poured to be placed in (100*100mm) Teflon mould and fills with the crystallising dish (125mm* of water
65mm) top, and covered completely with 3L beaker, vacuum drying is placed in until solvent volatilization finishes in 25 DEG C of evaporation acetone solvents
Polymer dielectric film can be obtained in case vacuum drying 12h, and evaporating temperature is generally slightly below the boiling temperature of solvent, so evaporation
Temperature is preferably 50 DEG C.Fig. 4 is the electron microscope of polymer dielectric film, it can be found that the porous side surface of polymer dielectric exists
Some 3~4 μm of micropores, by it is outer and it is interior there are the grading-holes of some different scales, being conducive to Electolyte-absorptive prevents electrolyte from letting out
Leakage；And at the polymer dielectric film back side, a small amount of duct is only existed, relatively flat, this has when contacting with lithium anode
Help inhibit the growth of Li dendrite.
Embodiment 5
Using polymer dielectric as middle-tier application solid-state secondary lithium battery electrode material and solid state electrolysis
Between matter phase, the cathode system in traditional lithium battery system is taken, using lithium metal as cathode, assembles CR2032 button cell.
Fig. 5 gives the overall structure diagram of the solid state battery.
Embodiment 6
By increasing the LAGP ceramics of decorative layer, (decorative layer is to infiltrate 1M LiPF6Pair of EC/DMC/DEC electrolyte
One polymer layer；It is about 1mm that potsherd, which is polishing to thickness, and diameter is about 14.5mm) current density be 0.05/cm-2It removes
It is tested with plating, it was demonstrated that the introducing of buffer layer increases LAGP to the stability of Li.As shown in Figure 6.
Embodiment 7
Constant current charge-discharge loop test is carried out to according to the CR2032 button cell of 5 structure of case and the assembling of embodiment 6.?
It is tested under room temperature, voltage range is 3~4.3V, carries out charge and discharge with 0.1C and 0.3C multiplying power.Figure (a) is complete solid
State battery first five week charging and discharging curve under 0.1C multiplying power；Figure (b) (c) is all-solid-state battery preceding 13 circle under 0.3C multiplying power respectively
Charging and discharging curve and battery long circulating performance map.As can be seen that battery can stable operation under different multiplying；At 0.3C times
Discharge capacity is 133.6mAh/g, capacity retention ratio 90.88% after circulating battery 150 encloses under rate.
Claims (7)
1. a kind of solid electrolyte LAGP powder, preparation NASICON structural chemistry general formula is LiN2(PO4)3, pass through element M part
Or conductivity is improved in the position of replacing whole N, general formula is Li1+xMxN2-x(PO4)3；
Wherein M is the metallic element of relatively low valence state, can be Al, Cr, Ga, Fe, Sc, In, Lu, one kind of the elements such as Y, La
Or it is a variety of；Preferably aluminium；
N can be the one or more of the elements such as Ti, Ge or V with the metal of relatively high valence state；Due to Ti4+Compare Ge4+More
Add and be easy to be restored by lithium metal, it is advantageous to be Ge；0 x≤2.5 <, most preferably x=0.5.
2. the preparation method of solid electrolyte LAGP powder described in accordance with the claim 1, which is characterized in that according to chemistry mole
Metering ratio weighs lithium source, the source M, the source N and phosphate, is dissolved in solvent A, after dispersing and dissolving is uniform, pH in mixing liquid is transferred to
Strong basicity, that is, pH is not less than 12, heats solvent evaporated after complete reaction, is completely dried to obtain crystalline solid, is fully ground and is placed on
In porcelain boat, moisture is set further to volatilize at a certain temperature, it is therefore preferable to 200~300 DEG C, after the completion of moisture evaporation, in high temperature
Under decompose phosphorus source, it is therefore preferable to 300 DEG C~400 DEG C, after obtained powder is repeatedly ground, at higher temperature lower preferably 800~
Calcining is carried out at 900 DEG C can be obtained NASICON type LAGP powder.
3. the preparation method of solid electrolyte LAGP powder according to claim 2, which is characterized in that the source Li is selected from
One hydronium(ion) lithia, anhydrous nitric acid lithium, lithium carbonate, lithium acetate or lithium oxalate；
The source M can be oxide, hydroxide, chlorate, nitrate；
Preferably, the source N, for example, germanium dioxide, tetraethoxy germanium, tetramethoxy germanium；
Preferably, the source P is selected from ammonium dihydrogen phosphate, diammonium hydrogen phosphate.
4. a kind of preparation of classifying porous polymer dielectric film, which is characterized in that make the hole of the film surface of preparation relatively
Greatly, more inward hole is smaller, and the polymer electrolyte is Kynoar, polyethylene glycol oxide, polyacrylonitrile, gathers inclined fluorine
Ethylene is total to the polymer such as hexafluoropropene, but not limited to this, preferably Kynoar is total to hexafluoropropene, specifically includes the following steps:
Polymer electrolyte is dissolved in solvent B by a certain percentage, solvent B such as acetone or n,N-Dimethylformamide, concentration
Between 98%~99%；Such as 50~60 DEG C of stirrings are sufficiently uniformly dissolved it at a certain temperature, add to mixing liquid
A certain amount of non-solvent phase stirring at normal temperature (non-solvent phase and solvent phase volume ratio are between 1:10 to 1:15), non-solvent are mutually for example gone
Ionized water or dehydrated alcohol after liquid to be mixed stirs evenly completely, prepare film on die substrate, it is slow to be first placed in room temperature
Evaporate solvent, be subsequently placed in 50~60 DEG C of vacuum oven vacuum drying until solvent be evaporated completely completely can be obtained it is classifying porous
Polymer dielectric film.Electrolyte film thickness is preferably that be close to the one side of die substrate between 50 to 100 μm be the face A, and exposure is empty
One side in gas is the face B, then the face B surface is porous structure, and more inward hole is smaller.
5. a kind of method for improving solid state battery interface stability using polymer dielectric and improving solid state battery performance, special
Sign is, is used as cushioning layer material using classifying porous polymer dielectric film prepared by claim 4, be placed in electrode material and
Between solid electrolyte described in claim 1, with positive electrode, electrolyte and lithium metal formed it is good contact, have
Effect reduces interface impedance, and can slow down the direct haptoreaction of solid electrolyte and lithium metal；Specifically include following methods:
(1) electrode prepares
Electrode material, binder are uniformly mixed with conductive additive with required mass ratio and are dissolved in solvent, is fully ground mixed
After closing uniformly, gained slurry is applied on a current collector, is completely dried；The preferably common Kynoar (PVDF) of binder, leads
Electric additive preferably uses carbon black, acetylene black or graphite etc., but is not limited to above-mentioned material；
(2) gel polymer electrolyte middle layer
Classifying porous polymer dielectric film prepared by claim 4 is cut into disk immersion electrolyte and fully absorbs, and
Extra electrolyte is dried with waterleaf paper；
(3) solid electrolyte potsherd
The solid electrolyte LAGP powder of claim 1 is pressed into tabletting, at high temperature, such as 850~950 DEG C of calcinings 10~
12h, and with sand paper sanding and polishing；
(4) solid state battery is constructed
Take the pole piece of step (1) as the anode in solid state battery, using negative electrode materials such as lithium metals as cathode, step (3)
Potsherd is as electrolyte, and thin polymer film is as the interface-modifying layer between anode and electrolyte ceramics piece in step (2)；Step
Suddenly electrolytic thin-membrane doubling (makes hole side inwardly, i.e., by classifying porous polymer dielectric film doubling, so that the face B and B in (2)
Face is close to, and the structure of ABBA is formed) as the interface-modifying layer between cathode of lithium and potsherd, and it is encapsulated in button cell shell
It is interior, pressurization to get arrive solid state battery sample.
6. according to the method for claim 5, which is characterized in that electrolytic thin-membrane doubling described in step (4) makes hole side
Inwardly, i.e., classifying porous polymer dielectric film doubling is formed into the structure of ABBA so that the face B and the face B are close to.
7. the solid state battery being prepared according to method described in claim 5 or 6.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110661032A (en) * | 2019-10-14 | 2020-01-07 | 中山大学 | Solid electrolyte film and application thereof |
| CN110797571A (en) * | 2019-10-25 | 2020-02-14 | 湖北万润新能源科技发展有限公司 | Preparation method and application of oxide solid electrolyte suitable for lithium iron phosphate material |
| CN111463478A (en) * | 2020-03-31 | 2020-07-28 | 珠海冠宇电池股份有限公司 | Solid-state battery comprising interface buffer layer and preparation method thereof |
| CN111463479A (en) * | 2020-04-10 | 2020-07-28 | 上海电气集团股份有限公司 | Solid electrolyte, composite solid electrolyte, lithium ion battery and preparation method and application thereof |
| CN112786950A (en) * | 2019-11-05 | 2021-05-11 | 中天储能科技有限公司 | Composite solid electrolyte, preparation method thereof and solid battery |
| CN113871723A (en) * | 2021-08-20 | 2021-12-31 | 佛山(华南)新材料研究院 | Solid electrolyte and preparation method thereof |
| CN113939940A (en) * | 2020-01-14 | 2022-01-14 | 株式会社Lg新能源 | Method for manufacturing all-solid battery including solid-liquid mixed electrolyte membrane, and solid-liquid mixed electrolyte membrane |
| CN114014965A (en) * | 2021-11-03 | 2022-02-08 | 上海电气集团股份有限公司 | Polymer film, electrolyte, all-solid-state battery, and preparation method and application thereof |
| CN114220944A (en) * | 2021-12-14 | 2022-03-22 | 天津巴莫科技有限责任公司 | Positive pole piece modified by polymer film and preparation method thereof |
| CN115483502A (en) * | 2022-07-22 | 2022-12-16 | 四川新能源汽车创新中心有限公司 | Protective film for improving interface stability of solid electrolyte and negative electrode, preparation method of protective film and solid battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110661032A (en) * | 2019-10-14 | 2020-01-07 | 中山大学 | Solid electrolyte film and application thereof |
| CN110797571A (en) * | 2019-10-25 | 2020-02-14 | 湖北万润新能源科技发展有限公司 | Preparation method and application of oxide solid electrolyte suitable for lithium iron phosphate material |
| CN112786950A (en) * | 2019-11-05 | 2021-05-11 | 中天储能科技有限公司 | Composite solid electrolyte, preparation method thereof and solid battery |
| CN113939940A (en) * | 2020-01-14 | 2022-01-14 | 株式会社Lg新能源 | Method for manufacturing all-solid battery including solid-liquid mixed electrolyte membrane, and solid-liquid mixed electrolyte membrane |
| CN111463478A (en) * | 2020-03-31 | 2020-07-28 | 珠海冠宇电池股份有限公司 | Solid-state battery comprising interface buffer layer and preparation method thereof |
| CN111463479A (en) * | 2020-04-10 | 2020-07-28 | 上海电气集团股份有限公司 | Solid electrolyte, composite solid electrolyte, lithium ion battery and preparation method and application thereof |
| CN111463479B (en) * | 2020-04-10 | 2022-11-22 | 上海电气集团股份有限公司 | Solid electrolyte, composite solid electrolyte, lithium ion battery, and preparation method and application thereof |
| CN113871723A (en) * | 2021-08-20 | 2021-12-31 | 佛山(华南)新材料研究院 | Solid electrolyte and preparation method thereof |
| CN114014965A (en) * | 2021-11-03 | 2022-02-08 | 上海电气集团股份有限公司 | Polymer film, electrolyte, all-solid-state battery, and preparation method and application thereof |
| CN114220944A (en) * | 2021-12-14 | 2022-03-22 | 天津巴莫科技有限责任公司 | Positive pole piece modified by polymer film and preparation method thereof |
| CN114220944B (en) * | 2021-12-14 | 2024-04-26 | 天津巴莫科技有限责任公司 | High polymer film modified positive electrode plate and preparation method thereof |
| CN115483502A (en) * | 2022-07-22 | 2022-12-16 | 四川新能源汽车创新中心有限公司 | Protective film for improving interface stability of solid electrolyte and negative electrode, preparation method of protective film and solid battery |
| CN115483502B (en) * | 2022-07-22 | 2023-12-05 | 四川新能源汽车创新中心有限公司 | Protective film for improving interface stability of solid electrolyte and negative electrode, preparation method of protective film and solid battery |
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