CN109742442A - The secondary cell of the preparation and application of the Garnet-type solid electrolyte solid electrolyte - Google Patents
The secondary cell of the preparation and application of the Garnet-type solid electrolyte solid electrolyte Download PDFInfo
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Abstract
The present invention relates to the preparation of Garnet-type solid electrolyte material, layer buffer design and this type solid electrolyte are applied to solid lithium ion secondary cell.The present invention can be used for all-solid lithium-ion battery, lithium-sulfur cell etc., play the role of electrolyte and diaphragm.Such solid electrolyte has the features such as macroion conductance, stability, chemical stability, electrochemical window mouth width, can simplify the preparation process of lithium ion battery, reduces cost, and can significantly improve the safety of battery.
Description
Technical field
The present invention relates to the preparation of carbuncle type lithium lanthanum zirconium oxygroup lithium ion conductor and solid state electrolysis composite materials
Preparation, and the lithium ion battery of the application solid electrolyte and its composite material.
Background technique
Lithium ion battery is one of portable, amusement, calculating and key component of telecommunication apparatus needed for today's society.Together
When with electronic product, electric car, New Energy Industry development, to the energy density of lithium ion battery, long circulating, safety
More stringent requirements are proposed for property.Lithium secondary battery based on liquid electrolyte, due to electrochemical stability, thermal stability, safety
The reasons such as property can not carry higher energy density and there are security risks.And use the solid lithium ion battery of solid electrolyte
There can be big advantage efficiently against above-mentioned shortcomings in terms of improving battery energy density and safety, be regarded
For one of next-generation most important energy storage technology.Wherein, not only itself has solid electrolyte and liquid electrolyte is comparable
Ionic conductivity, moreover it is possible to as battery separators, effectively the positive and negative electrode of battery be separated, in the life for simplifying traditional lithium battery
While producing preparation process, reduce cost, safety, operability and stability test are also greatly improved.Meanwhile it being based on
The conventional liquid lithium ion battery of lithium anode (lithium metal, lithium alloy) has great security risk and secondary disaster.
And after using solid state battery, solid lithium ion battery can preferably play the effect of lithium metal, and then battery may be implemented
High-energy density advantage.Therefore, have both superior performance and safety solid state battery be current educational circles and industrial circle it is diligent with
The target asked.According to the electrolyte used, solid state battery can be mainly divided into inorganic solid electrolyte battery and polymer battery
Deng.However the superior solid state battery of performance is developed at present, still suffer from many science and technology challenges: for example, electrode material body
Product variation, large interface (electrode/electrolyte) resistance, the low-load of electrode active material, cyclical stability difference and security performance
It is low.However among great number of issues, a major issue urgently to be solved is how to improve electrode and solid electrolyte interface
Between ionic conductivity, overcome these problems key be ion is produced between solid electrode and solid electrolyte can be with
Efficiently conduction and stable solid/solid interface, and this at least need to consider three aspect content: solid-state material it is wettable
The transmission rate of ion between property, the stability and interface at solid/solid interface.
The present invention is based on the Garnet-type solid electrolytes of preparation, have dexterously constructed positive and negative anodes and have connect with solid electrolyte
The buffer layer of touching, effective solution solid solid interface contact, thus the solid-state for realizing the high conductance of solid solid interface and constructing
Secondary cell excellent electrochemical performance.
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
The Garnet-type solid electrolyte of property and macroion conductance.The present invention also provides above-mentioned solid electrolyte and electrode material are compound
Obtained cushioning layer material is simultaneously applied in solid state battery system, and solid-solid interface compatibility issue is solved.Meanwhile the present invention is also
The solid lithium ion battery containing this carbuncle type oxide is constructed.
Realize that the object of the invention technical solution is as follows:
Illustrate technical solution of the present invention by taking Garnet-type solid electrolyte and lithium iron phosphate positive material as an example.
Garnet structure chemical general formula are as follows:
Li7-3x+y-zAxLa3-yByZr2-zCzO12
Wherein A can be the one or more of the elements such as Ga, Al；
B can be the one or more of the elements such as Ca, Sr, Ba, Ce；
C can be the one or more of the elements such as Ta, Nb, Ge, Sc, W, Zr, Hf, Sn, Sb, Te, using high valence elements into
When row doping, Li content can be regulated and controled, such as W, Te, Ta, Nb element；
X, y, z indicates molar ratio, it is preferable that 0≤x≤0.3, most preferably x=0.2；Preferably, 0≤y≤2；It is preferred that
Ground, 0 < z < 0.2；Li content can be regulated and controled by adjusting x, y, z value, it is preferable that Li content is 6.4.
The present invention provides a kind of Garnet-type solid electrolytes that A doping are prepared using sol-gal process
Li6.4Al0.2La3Zr2O12, lanthanum nitrate, lithium nitrate, aluminum nitrate, acetylacetone,2,4-pentanedione zirconium are weighed according to stoichiometric ratio, is dissolved in appropriate molten
Agent, such as water or ethyl alcohol.After being uniformly dispersed, the complexing agent citric acid and few drops of nitre for meeting metering ratio are added dropwise into mixing liquid
Acid heats solvent evaporated after complete reaction, is completely dried to obtain xerogel.It is fully ground to obtain grey powder, is placed in oxidation
In aluminium porcelain boat, at 500~600 DEG C, dumping process is completed.After the completion of dumping, ground again, at 800~900 DEG C into
Cubic phase LLZO powder can be obtained in row calcining.The temperature of cubic phase LLZO is generated generally 1000~1200 using solid phase method
DEG C, reaction temperature can be significantly reduced using sol-gal process in contrast.The preparation of such solid electrolyte is not limited to
Method in this.
Preferably, the source Li, for example, anhydrous nitric acid lithium, lithium carbonate, lithium acetate, lithium hydroxide or lithium oxalate；
Preferably, the source Al, for example, aluminum nitrate, aluminium chloride, aluminium oxide；
Preferably, the source Zr, for example, acetylacetone,2,4-pentanedione zirconium, ethyl alcohol zirconium, zirconyl nitrate；
Preferably, the source La, for example, lanthana, lanthanum nitrate, lanthanum chloride；
Compared with existing liquid electrolyte, Garnet-type solid electrolyte prepared by the present invention is had the following characteristics that
1. electrochemical window mouth width, the garnet-LLZO base solid electrolyte material of preparation is to Li metal negative electrode 0~6V's
Potential region is all electrochemically stable.
2. it is highly-safe, methanol can be generated in higher temperature decomposition relative to traditional organic electrolyte, hydrogen etc. is inflammable
Explosion hazard gases, Garnet-type electrolyte have very high stability, can be avoided dangerous generation.
3. chemical stability is high, it can directly be contacted with lithium metal, the electrochemically stable of solid solid interface can be significantly improved
Property and interface compatibility, and promote battery capacity.
Further, the present invention also provides the composite material of a kind of positive electrode and fast-ionic conductor, positive electrode aspects
It can be the positive electrodes such as stratiform cobalt acid lithium, LiFePO4, tertiary cathode material, cobalt acid sodium, but not limited to this.Solid electrolyte
Aspect can be the solid-states such as oxide solid electrolyte, sulfide solid electrolyte, LISICON, NASICON, Beta aluminium oxide
Electrolyte, but not limited to this.
Illustrate summary of the invention by taking Garnet-type solid electrolyte and LiFePO4 as an example:
Lanthanum nitrate, aluminum nitrate, lithium nitrate and acetylacetone,2,4-pentanedione zirconium are weighed according to stoichiometric ratio, is dissolved in appropriate solvent, such as water
Or ethyl alcohol.A certain amount of iron phosphate powder is added under stiring, obtains finely dispersed black suspension.It is dripped into mixing liquid
Add the complexing agent citric acid and few drops of nitric acid for meeting metering ratio, heats solvent evaporated after complete reaction, be completely dried and done
Gel.It is fully ground to obtain black powder, be placed in aluminium oxide porcelain boat, at 500~600 DEG C, complete dumping process.Dumping is complete
Cheng Hou is ground again, and calcining is carried out at 800~900 DEG C can be obtained the composite wood of solid electrolyte and electrode material
Material.
The present invention also provides a kind of construction methods of solid state battery.Specifically, the present invention utilizes the composite material prepared
It as cushioning layer material, is placed between positive electrode and solid electrolyte, is formed well with positive electrode, electrolyte respectively
Contact, interface impedance is effectively reduced.The design of specific solid state battery system and construct that steps are as follows:
(1) electrode prepares
The common positive and negative anodes collector of field of batteries is taken, by electrode material, binder and conductive additive are with certain matter
Amount is dissolved in appropriate solvent than uniformly mixing, is fully ground after mixing, 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) electrode material/composite material middle layer solid solid interface is constructed
Buffer layer composite material and PVDF are ground with certain proportion, appropriate solvent is added, make mixture it is evenly dispersed its
In.It takes the pole piece in step (1) stand-by, composite material dispersion liquid is coated on pole piece, is completely dried.
(3) composite material middle layer/solid electrolyte solid solid interface is constructed
After solid electrolyte is mixed with PVDF, appropriate solvent dispersion is added.Pole piece dried in step (2) is taken to wait for
With the dispersion liquid of solid electrolyte is coated in surface, is completely dried.
(4) solid state battery is constructed
Take the pole piece of step (3) as the anode in solid state battery, using negative electrode materials such as lithium metals as cathode, and to boundary
Face is activated, and is encapsulated in button cell shell, pressurization to get arrive solid state battery sample.
With macroion conductance, electrochemical window, high chemical/electrochemical stability Garnet-type solid electrolyte LLZO
It can satisfy the requirement of solid lithium ion battery.Solid electrolyte solid lithium ion battery based on this type is suitable for various storages
Energy equipment, such as can be applied to portable energy-storing equipment, electric car and electric tool, backup power supply, redundant electrical power, not
It is limited to this.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of Garnet-type solid electrolyte LLZO；
Fig. 2 is the X ray diffracting spectrum of composite material；
Fig. 3 is the ac impedance spectroscopy of Garnet-type solid electrolyte LLZO；
Fig. 4 is pattern of the Garnet-type solid electrolyte LLZO under scanning transmission electron microscope；
Fig. 5 is the schematic diagram for assembling all solid state lithium ion secondary cell；
Fig. 6 is the cyclic curve of all-solid-state battery；Fig. 7 is no buffer layer solid state battery charging and discharging curve；
Fig. 8 is the cyclic voltammetry curve of LLZO material
Specific embodiment
Case study on implementation 1
According to the characteristic of sol-gal process, it is preferable to use anhydrous nitric acid lithium, lanthanum nitrate hexahydrate, acetylacetone,2,4-pentanedione zirconium are as system
The source metal of standby LLZO.According to Li7La3Zr2O12Stoichiometric ratio weigh anhydrous nitric acid lithium (excessive 10% to 20%), six water
Lanthanum nitrate, acetylacetone,2,4-pentanedione zirconium are closed, and a small amount of aluminum nitrate is added, the solution and soluble in water equal with magnetic stirrer of being configured to
It is even.It is complexing agent citric acid is soluble in water and magnetic agitation is uniform, and few drops of 65% nitric acid are added in citric acid solution.To mixed
It closes in liquid and complexing agent is added dropwise, heat solvent evaporated after complete reaction, evaporating temperature is generally slightly below the boiling temperature of solvent,
So evaporating temperature is preferably 80 DEG C.As solvent evaporates, dark gel is obtained.Gained gel is dry in air dry oven
48h obtains xerogel.It is higher than the boiling point of water in the drying temperature in this stage, drying temperature is preferably 120 DEG C.Xerogel is ground
It after mill is uniform, is placed in aluminium oxide porcelain boat, at 600 DEG C, heat preservation 12h completes dumping process.After the completion of dumping, by gained powder
Regrinding uniformly, in 800 DEG C of heat preservation 12h, obtains cubic phase LLZO powder.Fig. 1 gives the X ray diffracting spectrum of LLZO,
It demonstrates and generates pure cubic phase, a cube phase structure ensure that high ionic conductivity.
Case study on implementation 2
Cushioning layer material preparation is similar with LLZO preparation flow.After metal salt is completely dissolved, a certain amount of ferric phosphate is added
Lithium powder obtains finely dispersed turbid.Complexing agent citric acid is soluble in water and magnetic agitation is uniform, and in citric acid solution
Few drops of 65% nitric acid are added.Complexing agent is added dropwise into mixing liquid, carries out complex reaction.Heating is evaporated molten after complete reaction
Agent, evaporating temperature is generally slightly below the boiling temperature of solvent, so evaporating temperature is preferably 80 DEG C.As solvent evaporates, obtain
Black gel.Gained gel is dried into 48h in air dry oven, obtains xerogel.It is higher than water in the drying temperature in this stage
Boiling point, drying temperature is preferably 100 DEG C.After xerogel grinding uniformly, it is placed in aluminium oxide porcelain boat, at 600 DEG C, heat preservation
12h completes dumping process.After the completion of dumping, gained powder is regrind uniformly, in 800 DEG C of heat preservation 12h, obtains buffer layer material
Material.Fig. 2 is the XRD spectrum of composite material, it is seen that LLZO cubic phase can be generated.
Case study on implementation 3
Inorganic solid electrolyte conductivity test generally with ceramic sheet form progress, potsherd both ends by sputtering or
Evaporation metal, such as Au.It is tested in this, as blocking electrode, since Au is to Li+With certain blocking action, therefore hindering
Apparent capacitive reactance arc is presented in the low frequency range of anti-spectrum.The potsherd prepared is polished, after LLZO potsherd surface gold-plating,
Ac impedance measurement has been carried out to LLZO potsherd.It is tested using EIS ac impedance spectroscopy.Frequency range be 0.1Hz~
1MHz, test temperature are room temperature.Map is as shown in figure 3, show that material prepared has low resistance, ionic conductance with higher
Rate.
Case study on implementation 4
Solid electrolyte material is observed under a scanning electron microscope and shows pattern and particle diameter distribution.What Fig. 4 gave
Experimental result shows that particle size distribution is uniform, more tiny compared to solid phase method particle.
Case study on implementation 5
Using composite material as middle-tier application solid-state secondary lithium battery electrode material phase and solid electrolyte
Between phase, using entire three-phase system as anode, take the cathode system in traditional lithium battery system, using lithium metal as bear
Pole assembles button cell.Fig. 5 gives the overall structure diagram of the solid state battery.
Case study on implementation 6
Constant current charge-discharge loop test is carried out to the solid state battery assembled according to 5 structure of case.It carries out at room temperature
Test, voltage range are 3~4.3V, carry out charge and discharge with 0.02C multiplying power.Fig. 6 gives with LiFePO4 and LLZO composite wood
Expect the charging and discharging curve of the solid lithium ion battery as buffer layer.
Case study on implementation 7
Remove buffer layer according to 5 structure of case, assembling compares test without the solid state battery of buffer layer.In room temperature item
It is tested under part, voltage range is 3~4.3V, carries out charge and discharge with 0.02C multiplying power.Fig. 7 gives no buffer layer solid-state electricity
Pond first lap charging and discharging curve.Battery can not work in following cycle, due to the anode contact poor with solid electrolyte, lithium from
Sub- transport capability is poor, shows extremely low capacity, the behavior of approximate capacitance.Demonstrate the important function of buffer layer.
Case study on implementation 8
Cyclic voltammetry is done to Li by LLZO, it was demonstrated that stability of the LLZO to Li.Wherein, there is Li- in 0.6V
The reduction peak of Al alloy.As shown in Figure 8.
Claims (8)
1. a kind of chemical general formula is Li7-3x+y-zAxLa3-yByZr2-zCzO12Garnet-type solid electrolyte, wherein A can be Ga,
The elements such as Al；B can be the one or more of the elements such as Ca, Sr, Ba, Ce；C can be Ta, Nb, Ge, Sc, W, Zr, Hf, Sn,
The elements such as Sb it is one or more.X, y, z indicates molar ratio, it is preferable that 0≤x≤0.3, most preferably x=0.2；It is preferred that
Ground, 0≤y≤2；Preferably, 0 < z < 0.2；Li can be regulated and controled by adjusting x, y, z value, it is preferable that Li content is 6.4.
2. electrolyte described in claim 1, which includes: according to Li7Al0.2La3Zr2O12The chemistry of middle element
Ratio is measured, by lanthanum source, silicon source, lithium source and zirconium source, solvent, such as dehydrated alcohol or water is added, stirs to being completely dissolved, obtains
A small amount of nitric acid and complexing agent citric acid is added in one solution under stiring, and solvent evaporated obtains gel, after being completely dried, grinds
Brown ceramic powder is heat-treated, and rises to 600 DEG C and at such a temperature preannealing 12h first with 2 DEG C/min of rate, cooling
Afterwards, it then is ground uniformly, then precursor powder is risen at 800 DEG C with 2 DEG C/min of rate and is annealed at such a temperature
12h is ground uniformly after cooling to get above-mentioned solid electrolyte material.But the preparation method of electrolyte is not limited to this.
3. element described in right 1 can be adulterated according to chemical general formula described in right 1,2 and solid electrolyte material preparation method
It optimizes, improves the ionic conductivity of material.Ga, Sc, Nb, the elements such as Ta are such as adulterated, but are not limited to the above element.
4. on the composite, solid electrolyte can with various types of electrodes Material cladding, just such as cobalt acid lithium, LiFePO4, ternary
Pole material, LiFePO4 etc., but not limited to this.It can be oxide solid electrolyte, sulfide solid-state in terms of solid electrolyte
The solid electrolytes such as electrolyte, LISICON, NASICON, Beta aluminium oxide, but not limited to this.Preparation method includes: to work as metal
After salt is completely dissolved, a certain amount of electrode material powder is added, obtains finely dispersed turbid.A certain amount of nitric acid is added under stiring
With complexing agent citric acid, solvent evaporated is heated after complete reaction, obtains gel.Gained gel drying is obtained into xerogel.It will do
It after gel abrasive is uniform, is placed in aluminium oxide porcelain boat, at 600 DEG C, heat preservation 12h completes dumping process.Again by gained powder
Grinding uniformly, in 800 DEG C of heat preservation 12h, obtains cushioning layer material.But preparation method is without being limited thereto.
5. electrode and composite material interface construction method include: by buffer layer according to composite material and preparation method thereof described in right 4
Material and binder are uniform with certain proportion grinding, and appropriate solvent is added, keeps mixture evenly dispersed wherein.By composite material
Dispersion liquid is coated in pole piece and is placed in drying in air dry oven.Slurry coating method is not limited to this.
6. the buffer layer that electrode material is constituted with composite material includes: with solid electrolyte interface construction method will be a certain proportion of
Solid electrolyte powder is uniformly mixed with binder, and appropriate N-Methyl pyrrolidone is added and makees solvent, keeps mixture evenly dispersed.
Pole piece is stand-by in weighting benefit 5, and the dispersion liquid of solid electrolyte is coated on surface and is placed in drying in drying box.
7. full battery construction method includes: that pole piece is as the anode in solid state battery in weighting benefit 6, with negative electrode materials such as lithium metals
It is activated, is encapsulated in button cell shell, pressurization is to get solid state battery as cathode, and to interface.Electrochemistry
Test scope is 3~4.3V, multiplying power 0.05C.
8. gained solid state battery can be used as energy storage device by described in right 7, it to be used for portable energy-storing equipment, electric car and electricity
Power driven tools, backup power supply, redundant electrical power, but not limited to this.
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Cited By (10)
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| CN110085910A (en) * | 2019-05-14 | 2019-08-02 | 中南大学 | Solid lithium battery, garnet solid electrolyte and preparation method thereof |
| CN110444805A (en) * | 2019-07-08 | 2019-11-12 | 电子科技大学 | A kind of the cubic phase Garnet-type solid electrolyte material and its synthetic method of Er ions |
| CN112038688A (en) * | 2020-08-19 | 2020-12-04 | 河南电池研究院有限公司 | Preparation method of one-dimensional nano-morphology LLZO-based solid electrolyte material |
| CN112531203A (en) * | 2020-12-10 | 2021-03-19 | 湖南艾华集团股份有限公司 | Solid electrolyte with high ionic conductivity and preparation method thereof |
| CN112601728A (en) * | 2019-07-19 | 2021-04-02 | 第一稀元素化学工业株式会社 | Ceramic powder material, method for producing ceramic powder material, and battery |
| CN114335738A (en) * | 2021-12-28 | 2022-04-12 | 中国科学院电工研究所 | Solid electrolyte and preparation method and application thereof |
| CN114628777A (en) * | 2021-05-29 | 2022-06-14 | 海南大学 | Preparation method of interface-modified solid electrolyte material |
| WO2022222493A1 (en) * | 2021-04-22 | 2022-10-27 | 海南大学 | Oxide-type solid electrolyte thin film and preparation method therefor |
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| CN110444805A (en) * | 2019-07-08 | 2019-11-12 | 电子科技大学 | A kind of the cubic phase Garnet-type solid electrolyte material and its synthetic method of Er ions |
| CN112601728A (en) * | 2019-07-19 | 2021-04-02 | 第一稀元素化学工业株式会社 | Ceramic powder material, method for producing ceramic powder material, and battery |
| EP3825282A4 (en) * | 2019-07-19 | 2021-11-17 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Ceramic powder material, method for producing ceramic powder material, and battery |
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| CN112038688B (en) * | 2020-08-19 | 2022-07-26 | 河南电池研究院有限公司 | Preparation method of LLZO-based solid electrolyte material with one-dimensional nano morphology |
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| WO2022222493A1 (en) * | 2021-04-22 | 2022-10-27 | 海南大学 | Oxide-type solid electrolyte thin film and preparation method therefor |
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| CN114335738A (en) * | 2021-12-28 | 2022-04-12 | 中国科学院电工研究所 | Solid electrolyte and preparation method and application thereof |
| CN116023134A (en) * | 2022-12-27 | 2023-04-28 | 合肥国轩高科动力能源有限公司 | Lithium lanthanum zirconium oxide material, preparation method thereof, solid electrolyte and solid lithium ion battery |
| CN116023134B (en) * | 2022-12-27 | 2024-01-19 | 合肥国轩高科动力能源有限公司 | Lithium lanthanum zirconium oxide material, preparation method thereof, solid electrolyte and solid lithium ion battery |
| CN116683021A (en) * | 2023-07-31 | 2023-09-01 | 国联汽车动力电池研究院有限责任公司 | Garnet-type oxide solid electrolyte, preparation method and application thereof |
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