CN110534802A - Solid electrolyte and its preparation method and application - Google Patents

Solid electrolyte and its preparation method and application Download PDF

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Publication number
CN110534802A
CN110534802A CN201910860043.XA CN201910860043A CN110534802A CN 110534802 A CN110534802 A CN 110534802A CN 201910860043 A CN201910860043 A CN 201910860043A CN 110534802 A CN110534802 A CN 110534802A
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Prior art keywords
solid electrolyte
ybr
lix
solid
comparative example
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Inventor
王格日乐图
谢尔盖·切尔诺夫
马忠龙
克劳迪乌·博格丹·布库尔
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of solid electrolyte and its preparation method and application, the general formula of the solid electrolyte is Li3MX6, wherein X is selected from Cl‑、Br‑、I‑、F‑、BF4 ‑、PF6 ‑、BOB‑, at least one of trifluoromethanesulp-onyl -onyl imide anion and double methyl fluoride sulfimide anion, M is selected from Sc3+、Y3+、La3+、Mo3+、B3+、Al3+、Ga3+、In3+And Fe3+At least one of.The solid electrolyte is soft, density is low, is easy to squeeze, and does not react with air or water, and ionic conductivity reaches 1.2mS/cm at room temperature, and electronic conductivity is down to 10‑9S/cm, oxidation stability and thermal stability are good, while low with the reactivity of electrode active material.

Description

Solid electrolyte and its preparation method and application
Technical field
The invention belongs to field of batteries, specifically, the present invention relates to solid electrolytes and its preparation method and application.
Background technique
Electric vehicle need battery can the chilling temperatures down to -30 DEG C or the hyperthermia temperature range greater than 45 DEG C and It charges in less than 30 minutes, is a biggish challenge for the battery of existing electric vehicle.Existing commercial Li-ion batteries master Will be using the liquid electrolyte with organic solvent, but the organic solvent in liquid electrolyte can become sticky at low temperature, and in height The lower volatilization of temperature.The increase of viscosity reduces the ionic conductivity of liquid electrolyte, and reduces safe charging rate.In addition, having The volatility and inflammability of solvent hamper the safety of battery, and can lead to fire or explosion.Current useful organic solvent Replace their commercial protocol with solid ionic conductor such as polymer or mineral crystal and glass with reduce battery windburn Danger.First generation solid lithium electrolyte includes the lithium salt solution or sulfide, oxidation of polyethylene oxide and polyvinylidene fluoride polymer The single ion inorganic conductor of object and phosphate base, such as LPS, LLZO and LATP race.Although can be mentioned using these solid conductors High battery security, but their performance is inferior to the battery with liquid electrolyte.In general, the battery with solid electrolyte is only It is had excellent performance at a high temperature of 40 DEG C or so.In addition, their energy density and charge rate, which are substantially less than, has liquid electrolytic The battery of matter.
Meanwhile in the preparation process of existing solid electrolyte, it is difficult to be processed into high surface area (> 15cm × 15cm) and 25 μm of thickness < of the film of high density (> 90%), and resulting film tensile strength is insufficient, can not be subjected to battery Assembling.The processing of existing solid electrolyte is limited to be sintered place under inert atmosphere and 1000 DEG C of temperature > of hot conditions Reason.In addition, i.e. commonly known as solid electrolyte interface (SEI) is not in the battery with liquid electrolyte to low resistance interface Can lack, and in the battery containing solid electrolyte, coating and guard electrode active material from solid state electrolysis qualitative response Research be still initial stage, and for commercialization for be not mature enough.
Therefore, existing solid electrolyte is further improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention One purpose is to propose a kind of solid electrolyte and its preparation method and application.The solid electrolyte is soft, density is low, It is easy to squeeze, is not reacted with air or water, and ionic conductivity reaches 1.2mS/cm at room temperature, electronic conductivity is down to 10-9S/cm, Oxidation stability and thermal stability are good, while low with the reactivity of electrode active material.
In one aspect of the invention, the invention proposes a kind of solid electrolytes, according to an embodiment of the invention, described The general formula of solid electrolyte is Li3MX6, wherein X is selected from Cl-、Br-、I-、F-、BF4 -、PF6 -、BOB-, trifluoromethanesulp-onyl -onyl imide At least one of anion and double methyl fluoride sulfimide anion, M is selected from Sc3+、Y3+、La3+、Mo3+、B3+、Al3+、Ga3+、 In3+And Fe3+At least one of.
Solid electrolyte according to an embodiment of the present invention, not sulfur-bearing, oxygen or phosphate ligand, and conducted with high lithium Property.It is soft simultaneously, density is low, is easy to squeeze, and do not reacted with air or water.Ionic conductivity reaches 1.2mS/ at room temperature Cm, electronic conductivity is down to 10-9S/cm, oxidation stability and thermal stability are good, while low with the reactivity of electrode active material.
In addition, solid electrolyte according to the above embodiment of the present invention can also have the following additional technical features:
In some embodiments of the invention, the X is selected from Cl-、Br-、I-And F-At least one of, M is selected from Y3+、Mo3 +、Al3+And Fe3+At least one of.
It is according to the present invention the invention proposes a kind of method for preparing solid electrolyte in another aspect of the present invention Embodiment, this method comprises:
According to stoichiometric ratio by LiX and MX3Mixed grinding；
Resulting mixture after the mixed grinding is sintered under an inert atmosphere, obtains solid electrolyte after cooling Li3MX6, wherein the LiX and MX3In X be selected from Cl-、Br-、I-、F-、BF4 -、PF6 -、BOB-, trimethyl fluoride sulfonyl it is sub- At least one of amine anion and double methyl fluoride sulfimide anion, the MX3In M be selected from Sc3+、Y3+、La3+、Mo3+、 B3+、Al3+、Ga3+、In3+And Fe3+At least one of.
The method according to an embodiment of the present invention for preparing solid electrolyte, by according to stoichiometric ratio by LiX and MX3It is mixed Grinding is closed, is conducive to improve LiX and MX3Contact area, while a small amount of LiX and MX can be made3Solid phase reaction occurs to generate Li3MX6；After mixture after mixed grinding is sintered under an inert atmosphere, raw material Li X and MX can be made3Carry out high temperature solid-state reactions And it reacts sufficiently, the Li of corresponding amount is generated according to stoichiometric ratio3MX6, solid electrolyte Li is obtained after cooling3MX6.Invention People has been surprisingly found that the technique that this method is combined by using simple grinding and sintering was both easy to implement by many experiments Industrialized production, and can be prepared that soft, density is low, be easy to squeeze, purity is high, ionic conductivity reaches 1.2mS/ at room temperature Cm, electronic conductivity are down to 10-9The good and reactivity with electrode active material of S/cm, oxidation stability and thermal stability is low to be consolidated State electrolyte.
In addition, the method according to the above embodiment of the present invention for preparing solid electrolyte can also have following additional skill Art feature:
In some embodiments of the invention, the time of the mixed grinding is 1-2h.
In some embodiments of the invention, the temperature of the sintering is not more than 800 DEG C, time 10-60h.
In some embodiments of the invention, the temperature of the sintering is 550-800 DEG C, time 10-60h.
In some embodiments of the invention, described be sintered to is warming up to 750 DEG C from 200 DEG C with the speed of 5 DEG C/min, burns Tie 10-60h.
In some embodiments of the invention, described to be cooled to be cooled to 200 DEG C with the speed of 5 DEG C/min.
In some embodiments of the invention, the LiX and MX3Purity independently be not less than 95%.
In an additional aspect of the present invention, the invention proposes a kind of solid state batteries, according to an embodiment of the invention, this is solid State battery has above-mentioned solid electrolyte.Because the solid electrolyte is soft, is easy to squeeze, so that solid electrolyte can be according to battery Requirement flexible transformation specific form, significantly improve the applicability of the solid electrolyte；Simultaneously because of the solid electrolyte purity Height, ionic conductivity reaches 1.2mS/cm at room temperature, and electronic conductivity is down to 10-9S/cm, it is low with the reactivity of electrode active material, So that the battery has preferable charge-discharge performance；Further, because of the oxidation stability of the solid electrolyte and thermal stability It is good, be conducive to improve solid state battery to the adaptability of environment, avoid the hair for leading to the accidents such as solid state battery explosion because temperature is excessively high It is raw, while battery performance caused by can avoid because of oxidative environment damages problem.
In an additional aspect of the present invention, the invention proposes a kind of vehicles, according to an embodiment of the invention, the vehicle has There is above-mentioned solid state battery.The solid state battery has preferable charge-discharge performance, while to the adaptable of environment, enables vehicle The adaptability of environment is improved while with higher mileage number.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow schematic diagram according to an embodiment of the invention for preparing solid electrolyte；
Fig. 2 is embodiment 1 and the resulting solid electrolyte Li of comparative example 13YBr6With YBr3XRD spectrum；
Fig. 3 is embodiment 1 and the resulting solid electrolyte Li of comparative example 13YBr6With [6-319] Li Br/LiBr, [49- 959] XRD spectrum of Li Br/LiBr；
Fig. 4 (a) is and the resulting Li containing comparative example 13MBr6Cathode circulation after indium anode in Br X-ray energy spectrum Analyze signal graph；
Fig. 4 (b) is and the resulting Li containing comparative example 13MBr6Cathode circulation after indium anode in Y X-ray energy spectrum point Analyse signal graph；
Fig. 4 (c) is and the resulting Li containing comparative example 13MBr6Cathode circulation after indium anode in In X-ray energy spectrum Analyze signal graph；
Fig. 5 is in Li/Li battery plating/strip cycles by the resulting Li of comparative example 13YBr6Remove resulting voltage- Time, current versus time curve figure；
Fig. 6 is in Li/Li battery plating/strip cycles by the resulting Li of comparative example 13YBr6The CV of removing recycles bent Line chart；
Fig. 7 is the resulting solid electrolyte Li containing comparative example 13YBr6Li/NMC811 battery first circulation curve graph；
Fig. 8 is the resulting solid electrolyte Li containing comparative example 13YBr6In/NMC811 circulating battery curve graph；
Fig. 9 (a) is 1 gained solid electrolyte Li of embodiment3YBr6Impedance spectra；
Fig. 9 (b) is the partial enlarged view of Fig. 9 (a)；
Figure 10 is 1 gained solid electrolyte Li of embodiment3YBr6Electronic conductivity test in current-vs-time relational graph；
Figure 11 is 1 gained solid electrolyte Li of embodiment3YBr6Differential Scanning Calorimetry thermal stability curve graph；
Figure 12 is embodiment 1 and comparative example 4,5 gained solid electrolyte Li of comparative example3YBr6Oxidation stability curve graph.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the invention proposes a kind of solid electrolytes, according to an embodiment of the invention, this is solid The general formula of state electrolyte is Li3MX6, wherein X can be selected from Cl-、Br-、I-、F-、BF4 -、PF6 -、BOB-, trimethyl fluoride sulfonyl it is sub- At least one of amine anion and double methyl fluoride sulfimide anion, preferably Cl-、Br-、I-And F-At least one of, M Sc can be selected from3+、Y3+、La3+、Mo3+、B3+、Al3+、Ga3+、In3+And Fe3+At least one of, preferably Y3+、Mo3+、Al3+With Fe3+At least one of.Inventors have found that the performance of existing solid electrolyte includes that energy density and charge rate are inferior to mostly Liquid electrolyte, and thermal stability is poor, while the surface area of industrialized solid electrolyte is smaller, density is lower, thickness compared with Greatly, tensile strength is inadequate, and the more difficult battery assembly that withstands is without breakage.Inventor proposes general formula after many experiments For Li3MX6Above-mentioned solid electrolyte, not sulfur-bearing, oxygen or phosphate ligand, and find it with high lithium through many experiments Conductibility, at the same it is soft, density is low, is easy to squeeze, and does not react with air or water, ionic conductivity reaches at room temperature 1.2mS/cm, electronic conductivity is down to 10-9S/cm, oxidation stability and thermal stability are good, while anti-with electrode active material Answering property is low.
In another aspect of the invention, the invention proposes a kind of methods for preparing above-mentioned solid electrolyte, according to this The embodiment of invention, with reference to Fig. 1, this method comprises:
S100: according to stoichiometric ratio by LiX and MX3Mixed grinding
In the step, according to stoichiometric ratio by LiX and MX3Mixed grinding.Inventors have found that by according to stoichiometry Than by LiX and MX3Mixed grinding is conducive to improve LiX and MX3Contact area, improve the extent of reaction, while can make a small amount of LiX and MX3Reaction generates Li3MX6。
According to one embodiment of present invention, X can be selected from Cl-、Br-、I-、F-、BF4 -、PF6 -、BOB-, trifluoromethyl sulphur At least one of imide anion and double methyl fluoride sulfimide anion, M can be selected from Sc3+、Y3+、La3+、Mo3+、B3 +、Al3+、Ga3+、In3+And Fe3+At least one of.Further, LiX and MX3Purity can independently be not less than 95%, for example, LiX, MX that LiX can be 99.0% for anhydrous and purity3The MX that can be 99.99% for anhydrous and purity3。 Further, the time of mixed grinding can be 1-2h, such as can be 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2.0h.Invention People discovery, the technical solution which synthesize relative to existing ball milling, the time significantly reduce, while by grinding LiX and MX3Solid phase reaction can occur, generate a small amount of Li3MX6。
S200: mixture resulting after mixed grinding is sintered under an inert atmosphere
In the step, mixture resulting after mixed grinding is sintered under an inert atmosphere, obtains solid-state after cooling Electrolyte Li3MX6.Inventors have found that after the mixture after mixed grinding is sintered under an inert atmosphere, can make raw material Li X with MX3It carries out high temperature solid-state reactions and reacts sufficiently, the Li of corresponding amount is generated according to stoichiometric ratio3MX6, consolidated after cooling State electrolyte Li3MX6.Further, inventor has been surprisingly found that by many experiments, this method by using simple grinding and It is sintered the technique that combines, is not only easy to implement industrialized production, but also can be prepared that soft, density is low, is easy to squeeze, and is pure Degree is high, and ionic conductivity reaches 1.2mS/cm at room temperature, and electronic conductivity is down to 10-9S/cm, oxidation stability and thermal stability are good, The low solid electrolyte with the reactivity of electrode active material.Meanwhile inventor also studied using the preparation of ball mill ball milling admittedly State electrolyte Li3MX6Method, but many experiments find, to make LiX and MX by ball milling3The extent of reaction it is higher, together When obtain the higher solid electrolyte Li of conductivity3MX6, rotational speed of ball-mill must be very high, is greater than 600rpm.And existing work Few to reach the revolving speed in the ball mill that industry uses, can reach the revolving speed is low capacity mostly, is unable to satisfy The demand of industrialized production.
According to one embodiment of present invention, the temperature of sintering can be not more than 800 DEG C, and the time can be 10-60h.Hair Bright people discovery, the temperature relative to it is existing need to greater than 1000 DEG C at a temperature of the technique that is sintered for, temperature significantly drops It is low, but ionic conductivity reaches 1.2mS/cm to the solid electrolyte for being sintered out at room temperature, and electronic conductivity is down to 10-9S/cm, Oxidation stability and thermal stability are good, while low with the reactivity of electrode active material.Further, the temperature of sintering can be 550-800 DEG C, such as can be 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, the time can be 10-60h.Invention People has been surprisingly found that sintering is conducive to improve LiX and MX within the scope of above-mentioned temperature and time by many experiments3Solid phase reaction Rate, while improving solid electrolyte Li3MX6Quality.Further, sintering can be risen with the speed of 5 DEG C/min from 200 DEG C Temperature is sintered 10-60h, such as sintering 10h, 20h, 30h, 40h, 50h, 60h to 750 DEG C.Inventor surprisingly sends out by many experiments It is existing, LiX and MX can further improve using above-mentioned heating form3Solid phase reaction rate, while improving solid electrolyte Li3MX6 Quality.Further, cooling can be cooled to 200 DEG C with the speed of 5 DEG C/min.Be conducive to maintain solid electrolyte as a result, Li3MX6The stability of quality.Further, inert atmosphere can be nitrogen or argon gas, while during the sintering process, inert gas Flow be not particularly restricted, those skilled in the art can select according to actual needs.
Further, according to an embodiment of the invention, the solid electrolyte being prepared using the above method of the application, By X ray diffracting spectrum it is found that solid electrolyte Li3MX6In be substantially free of raw material Li X and MX3, i.e. LiX and MX3Reaction is abundant. And use same materials LiX and MX3But using the common planetary formula ball of different rotating speeds (including 200rpm, 400rpm, 600rpm) Grinding machine or the non-planetary high-energy ball mill ball milling of Emax from Retsch synthesize resulting solid electrolyte Li3MX6In, it is former The extent of reaction of material is unable to reach 100%.The conductance for the solid electrolyte being prepared simultaneously using the above method of the application Rate is relative to using same materials LiX and MX3But using the common row of different rotating speeds (including 200rpm, 400rpm, 600rpm) Planetary ball mill or the non-planetary high-energy ball mill ball milling of Emax from Retsch synthesize the electricity of resulting solid electrolyte Conductance is relatively relatively low.According to a particular embodiment of the invention, using LiBr and MBr3For raw material, using different rotating speeds (including 200rpm, 400rpm, 600rpm) common planetary formula ball mill or the non-planetary high-energy ball mill of Emax from Retsch Ball milling composite solid state electrolyte Li3MX6The extent of reaction and conductivity it is as shown in table 1.As shown in Table 1, revolving speed is to raw material reaction interval The influence of degree and conductivity, the extent of reaction increase with the increase of drum's speed of rotation, similarly, final gained solid electrolyte Conductivity also increases with rotational speed of ball-mill and is increased.
LiBr and MBr under 1 Different Preparation of table3The extent of reaction and gained solid electrolyte conductivity
It should be noted that, although solid electrolyte Li3MX6It can be synthesized by ball milling, but be suitble to business application at present The revolving speed of ball mill is limited in lower range.Minority has the business ball mill of the big tank of 1L capacity can be to be higher than The speed of 400rpm rotates, and the revolving speed of the ball mill of most of large capacity is 200rpm.As shown in Table 1, it uses at the low rotational speed The solid electrolyte of ball mill synthesis shows lower conductivity and the raw material extent of reaction.It is former when revolving speed is more than 600rpm The XRD signal of material reduces or does not have.Unfortunately, can atwirl ball mill usually only there is small tank, such as 50ml Or it is less, it is unsuitable for large-scale business application.
The method according to an embodiment of the present invention for preparing solid electrolyte, by according to stoichiometric ratio by LiX and MX3It is mixed Grinding is closed, is conducive to improve LiX and MX3Contact area, while a small amount of LiX and MX can be made3Reaction generates Li3MX6；Mixing After mixture after grinding is sintered under an inert atmosphere, raw material Li X and MX can be made3It carries out high temperature solid-state reactions and reacts to fill Point, the Li of corresponding amount is generated according to stoichiometric ratio3MX6, solid electrolyte Li is obtained after cooling3MX6.Inventor is by a large amount of Experiment has been surprisingly found that the technique that this method is combined by using simple grinding and sintering is both easy to implement industrialized production, It can be prepared that soft, density is low, is easy to squeeze again, and purity is high, ionic conductivity reaches 1.2mS/cm, electronics electricity at room temperature Conductance is down to 10-9S/cm, oxidation stability and thermal stability are good, the low solid electrolyte with the reactivity of electrode active material.
In an additional aspect of the present invention, the invention proposes a kind of solid state batteries, according to an embodiment of the invention, this is solid State battery has above-mentioned solid electrolyte.Because the solid electrolyte is soft, is easy to squeeze, so that solid electrolyte can be according to battery Requirement flexible transformation specific form, significantly improve the applicability of the solid electrolyte；Simultaneously because of the solid electrolyte purity Height, ionic conductivity reaches 1.2mS/cm at room temperature, and electronic conductivity is down to 10-9S/cm, it is low with the reactivity of electrode active material, So that the battery has preferable charge-discharge performance；Further, because of the oxidation stability of the solid electrolyte and thermal stability It is good, be conducive to improve solid state battery to the adaptability of environment, avoid the hair for leading to the accidents such as solid state battery explosion because temperature is excessively high It is raw, while battery performance caused by can avoid because of oxidative environment damages problem.
In an additional aspect of the present invention, the invention proposes a kind of vehicles, according to an embodiment of the invention, the vehicle has There is above-mentioned solid state battery.The solid state battery has preferable charge-discharge performance, while to the adaptable of environment, enables vehicle The adaptability of environment is improved while with higher mileage number.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe Property, without limiting the invention in any way.
Embodiment 1
The YBr for being 99.99% with anhydrous and purity by the LiBr that anhydrous and purity is 99.0% according to stoichiometric ratio3It is mixed Close grinding 1-2h；Then mixture resulting after mixed grinding is heated up with the speed of 5 DEG C/min from 200 DEG C in a nitrogen atmosphere To 750 DEG C, sintering for 24 hours, is then cooled to the flaky material that white glassy/wax-like is obtained after 200 DEG C with the speed of 5 DEG C/min Solid electrolyte Li3YBr6, the material softness, when suppress it is thin when can form translucent pellet.Its XRD spectrum such as Fig. 2 and 3 institute Show.As shown in Figure 2, in solid electrolyte Li3YBr6In, YBr is not present3Map, i.e. YBr3Fully reacting.From the figure 3, it may be seen that In Solid electrolyte Li3YBr6In, LiBr map, i.e. LiBr fully reacting is not present.That is solid electrolyte Li3YBr6With height Purity.Simultaneously by solid electrolyte Li between stainless steel electrode3YBr6Be pressed into bead, impedance spectrum as shown in figure 9, by Fig. 9 is it is found that solid electrolyte Li at room temperature3YBr6Conductivity be 1.2mS/cm.Further, to the solid state electrolysis Matter Li3YBr6Electronic conductivity test is carried out, specifically, grain thickness is 300 μm, area 0.785cm2, test voltage is Steady-state current after 2V, 1min is 0.24 μ A.The relational graph of gained electric current at any time is as shown in Figure 10, by Figure 10 calculate it is found that Solid electrolyte Li3YBr6Electronic conductivity be 10-9S/cm.Further, to solid electrolyte Li3YBr6Carry out heat Stability test, Differential Scanning Calorimetry thermal stability is as shown in figure 11, as shown in Figure 11, solid electrolyte Li3YBr6In It is still stable at up to 500 degrees Celsius.Further, oxidation stability is as shown in figure 12.
Comparative example 1
The YBr for being 99.99% with anhydrous and purity by the LiBr that anhydrous and purity is 99.0% according to stoichiometric ratio3It send The common planetary formula ball mill ball milling 120h for being 400rpm to revolving speed obtains the solid electrolyte that conductivity is 0.2mS/cm Li3YBr6.And gained Li3YBr6Mass ratio with LiBr is 1.8:1, the extent of reaction of LiBr about 50%.
Its XRD spectrum is as shown in Figures 2 and 3.As shown in Figure 2, in solid electrolyte Li3YBr6In, YBr3Map still may be used See, i.e. YBr3Reaction is incomplete.From the figure 3, it may be seen that in solid electrolyte Li3YBr6In, LiBr map is still visible and has higher Ratio, i.e. LiBr reaction is incomplete.
Comparative example 2
The YCl for being 99.99% with anhydrous and purity by the LiCl that anhydrous and purity is 99.0% according to stoichiometric ratio3It send The common planetary formula ball mill ball milling 120h for being 400rpm to revolving speed obtains the solid electrolyte that conductivity is 0.1mS/cm Li3YCl6.And gained Li3YCl6Mass ratio with LiCl is 1:4.3, and the extent of reaction of LiCl is less than 20%.
Comparative example 3
The YI for being 99.99% with anhydrous and purity by the LiI that anhydrous and purity is 99.0% according to stoichiometric ratio3Send to Revolving speed is the common planetary formula ball mill ball milling 120h of 400rpm, obtains the solid electrolyte Li that conductivity is 0.8mS/cm3YI6。 And gained Li3YI6Mass ratio with LiI is 1:0, and the extent of reaction of LiI is 100%, there is a small amount of YI3It retains.
Comparative example 4
The YBr for being 99.99% with anhydrous and purity by the LiBr that anhydrous and purity is 99.0% according to stoichiometric ratio3It send The common planetary formula ball mill ball milling 120h for being 350rpm to revolving speed obtains the solid electrolyte that conductivity is 0.1mS/cm Li3YBr6.Its oxidation stability is as shown in figure 12.
Comparative example 5
The YBr for being 99.99% with anhydrous and purity by the LiBr that anhydrous and purity is 99.0% according to stoichiometric ratio3It send The common planetary formula ball mill ball milling 40h for being 600rpm to revolving speed obtains the solid electrolyte that conductivity is 0.8mS/cm Li3YBr6.Its oxidation stability is as shown in figure 12.
By comparative example 1-3 it is found that under the rotational speed of ball-mill of identical 400rpm, the journey of the iodide reaction progress of comparative example 3 Degree is higher than the bromo-reaction of comparative example 1, and the degree that the bromo-reaction of comparative example 1 carries out is higher than the chlorination of comparative example 2 again.I.e. The extent of reaction is set to reach 100%, energy > bromo-reaction > iodide reaction needed for chlorination.That is the tool of halogen element ion Body type is determined compared with LiX under the slow-speed of revolution and MX3The extent of reaction.
In comparative example 1 and comparative example 2, although unreacted LiBr, LiCl may be decreased conductivity, because LiBr, LiCl is stable in lithium metal, and can form passivating film, will not generate negative shadow to the Reductive stability of lithium metal It rings.However, YBr3、YCl3It is strong lewis acid, has and be ready to connect nucleophobic unoccupied orbital.Therefore, YBr3、YCl3Low Voltage or there are lithium metal in the case where be easy reduction.By comparative example 1 and comparative example 2 it is found that the resulting Li of comparative example 13YBr6Than The resulting Li of comparative example 23YCl6With higher conductivity.
To the resulting Li of comparative example 13YBr6Further studied.Specifically, at low voltage, indium anode with containing pair The resulting Li of ratio 13MBr6Cathode circulation after X-ray energy spectrum analysis signal as shown in figure 4, in order to preferably analyze It is scraped among indium anode.As shown in Figure 4, indium anode with contain above-mentioned Li3MBr6After the cathode circulation of solid electrolyte With the Y and Br of trace on indium anode, shows to exist and decompose, produce a small amount of Y and Br.Because of Li3MBr6In contain high-content Unreacted YBr3, YBr3It is a kind of lewis acid, is easy to be restored, and this property easily restored may be to cause The reason of above-mentioned decomposition.That is the product Li of ball-milling reaction generation3MX6Containing different amounts of unreacted lewis acid, which reduce Product Li3MX6Total Reductive stability.In order to make solid electrolyte Li3MX6Voltage stability window maximize, it is important to drive Fully reacting carries out, to remove unreacted starting material such as YCl3Lewis acid.
With the resulting Li of comparative example 13YBr6For, in Li/Li battery plating/strip cycles, by 1 institute of comparative example The Li obtained3YBr6Removing, experiment area are 0.785cm2, the relationship of voltage, electric current at any time is as shown in figure 5, CV cyclic curve As shown in Figure 6.As shown in Figure 5, Li/Li battery shows the overpotential being slightly increased in plating/strip cycles.It can by Fig. 6 Know, reversible plating, Li can occur for Li3YBr6With the high oxidation stability higher than 5V relative to Li.
In room temperature and under conditions of discharge rate is C/10, to the resulting solid electrolyte Li containing comparative example 13YBr6Li/ NMC811 battery carries out first circulation, wherein assembling pressure 400MPa tests pressure about 1MPa, the thickness of NMC811 cathode It is 50 μm, NMC811: solid electrolyte Li3YBr6: the ratio of C is 70:29:1, and conductive diaphragm is with a thickness of 400 μm.Obtain NCM811 The theoretical capacity of active material is as shown in Figure 7.As shown in Figure 7, Li/NMC811 full battery may be the reactivity due to Li anode Increase is unable to good circulation.However, NMC811 cathode can recycle together with In anode.In room temperature and discharge rate is C/10's Under the conditions of, to the resulting solid electrolyte Li containing comparative example 13YBr6In/NMC811 battery recycled, as a result such as Fig. 8 institute Show.Wherein, assembling pressure 400MPa, tests pressure about 1MPa, NMC811 cathode with a thickness of 50 μm, NMC811: solid-state electricity Solve matter Li3YBr6: the ratio of C is 70:29:1, and conductive diaphragm is with a thickness of 400 μm.As shown in Figure 8, the reduction potential ratio Li of In also The high 0.7V of former current potential, and the reactivity of In is lower, this and the resulting solid electrolyte Li of comparative example 13YBr6In still have YBr3Lewis acid is related.Meanwhile the reduction potential of In is also slightly above the reduction potential of Y, it can be from YBr3It is middle to exclude undesirable electricity Plate yttrium metal.
As shown in Figure 12, comparative example 1 and comparative example 4, comparative example 5, in the common planetary formula ball mill ball of 350rpm Grind resulting solid electrolyte Li3YBr6With minimum oxidation stability, this may be since unreacted material content is high. And the common planetary formula ball mill ball milling of 600rpm and the solid electrolyte Li being prepared using the application preparation method3YBr6 Stability with higher, and the solid electrolyte Li being prepared using the present processes3YBr6It is most stable of.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned Embodiment is changed, modifies, replacement and variant.

Claims (10)

1. a kind of solid electrolyte, which is characterized in that the general formula of the solid electrolyte is Li3MX6, wherein X is selected from Cl-、Br-、 I-、F-、BF4 -、PF6 -、BOB-, in trifluoromethanesulp-onyl -onyl imide anion and double methyl fluoride sulfimide anion at least it One, M are selected from Sc3+、Y3+、La3+、Mo3+、B3+、Al3+、Ga3+、In3+And Fe3+At least one of.
2. solid electrolyte according to claim 1, which is characterized in that the X is selected from Cl-、Br-、I-And F-In at least One of, M is selected from Y3+、Mo3+、Al3+And Fe3+At least one of.
3. a kind of method for preparing solid electrolyte of any of claims 1 or 2 characterized by comprising
According to stoichiometric ratio by LiX and MX3Mixed grinding；
Resulting mixture after the mixed grinding is sintered under an inert atmosphere, obtains solid electrolyte after cooling Li3MX6, wherein the LiX and MX3In X be selected from Cl-、Br-、I-、F-、BF4 -、PF6 -、BOB-, trimethyl fluoride sulfonyl it is sub- At least one of amine anion and double methyl fluoride sulfimide anion, the MX3In M be selected from Sc3+、Y3+、La3+、Mo3+、 B3+、Al3+、Ga3+、In3+And Fe3+At least one of.
4. according to the method described in claim 3, it is characterized in that, the time of the mixed grinding is 1-2h.
5. according to the method described in claim 3, it is characterized in that, the temperature of the sintering be not more than 800 DEG C, time 10- 60h；
Optional, the temperature of the sintering is 550-800 DEG C, time 10-60h.
6. according to the method described in claim 5, it is characterized in that, described be sintered to is heated up with the speed of 5 DEG C/min from 200 DEG C To 750 DEG C, it is sintered 10-60h.
7. according to the method described in claim 3, it is characterized in that, described be cooled to be cooled to 200 with the speed of 5 DEG C/min ℃。
8. according to the method described in claim 3, it is characterized in that, the LiX and MX3Purity independently not small In 95%.
9. a kind of solid state battery, which is characterized in that the solid state battery include solid electrolyte of any of claims 1 or 2 or The solid electrolyte being prepared using method described in any one of claim 3-8.
10. a kind of vehicle, which is characterized in that the vehicle includes solid state battery as claimed in claim 9.
CN201910860043.XA 2019-09-11 2019-09-11 Solid electrolyte and its preparation method and application Pending CN110534802A (en)

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CN113845141A (en) * 2020-06-28 2021-12-28 宝山钢铁股份有限公司 Fluorine-doped halide solid electrolyte, preparation method and lithium battery
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CN114122503A (en) * 2020-08-27 2022-03-01 比亚迪股份有限公司 Solid electrolyte, preparation method thereof and battery
CN114864944A (en) * 2022-05-18 2022-08-05 天津中能锂业有限公司 Metal lithium belt with porous solid electrolyte layer and preparation method thereof

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Application publication date: 20191203