CN110289445A - A kind of LiCuLaZrMO method for preparing solid electrolyte - Google Patents
A kind of LiCuLaZrMO method for preparing solid electrolyte Download PDFInfo
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- 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
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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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- 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
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Abstract
The present invention relates to a kind of LiCuLaZrMO method for preparing solid electrolyte, comprising the following steps: by La2O3、ZrO2, copper compound, M compound and lithium salts mixing, be added dispersing agent, by grinding, being dried to obtain presoma；By presoma in 300~809 DEG C of calcination process, it is cooled to room temperature, grinds, obtains LiCuLaZrMO powder；LiCuLaZrMO powder tabletting is obtained into LiCuLaZrMO piece with tablet press machine, LiCuLaZrMO powder is added in calcination vessel, the LiCuLaZrMO piece is inserted into LiCuLaZrMO powder, is sintered at 1000~1159 DEG C, it is cooled to room temperature, obtains the LiCuLaZrMO solid electrolyte.Compared with prior art, the present invention has many advantages, such as that preparation method is simple, synthesis temperature is low, energy saving.
Description
Technical field
The invention belongs to electrochemical technology fields, more particularly, to a kind of preparation side of LiCuLaZrMO solid electrolyte
Method.
Background technique
All-solid lithium-ion battery due to high security, have extended cycle life, energy density is high, use temperature range is wide
The features such as, become the hot spot studied now, solid electrolyte is one of core of all-solid lithium-ion battery.Solid electrolytic
High temperature solid phase synthesis is commonly used in the preparation of matter, and synthesis temperature is higher, and temperature is probably at 1600 DEG C or more；Higher synthesis temperature is made
At preparation condition harshness, the lectotype selection being unfavorable in expanded production and production process.
Chinese patent CN106684440A discloses a kind of LiBaLaZrWREAlO method for preparing solid electrolyte；With
La2O3、ZrO2、WO3, rare earth oxide, Al2O3It is raw material with lithium-containing compound, first time maturing temperature is 810~990 DEG C, the
After baking temperature is 1160~1200 DEG C；Chinese patent CN106025349A discloses a kind of LiBaLaZrREAlO solid electricity
The preparation method of matter is solved, with La2O3、ZrO2, rare earth oxide, Al2O3It is raw material with lithium-containing compound, first time maturing temperature is
810~990 DEG C, second of maturing temperature is 1160~1200 DEG C；Chinese patent CN106159319A discloses one kind
The preparation method of LiBaLaZrAlREWO lithium ion solid electrolyte, this method first time maturing temperature are 810~990 DEG C, the
After baking temperature is 1160~1200 DEG C；And Chinese patent CN105977531A discloses a kind of LiBaLaZrAlREO lithium
Ion solid electrolyte preparation method, this method first time maturing temperature are 810~990 DEG C, and second of maturing temperature is
1160~1200 DEG C.The maturing temperature of these patents is also further reduced space；In synthesis process, some preparation methods
Preparation route, preparation method are complicated；And there are also further for the lithium ion conductivity of solid electrolyte obtained in these patents
Raising space.
Summary of the invention
It is solid that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of LiCuLaZrMO
Body electrolyte preparation method.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of LiCuLaZrMO method for preparing solid electrolyte, comprising the following steps:
(1) by La2O3、ZrO2, copper compound, M compound and lithium salts mixing, be added dispersing agent, by grinding, drying
To presoma；
(2) by calcination process at 300~809 DEG C of presoma in step (1), it is cooled to room temperature, grinds, obtain
LiCuLaZrMO powder；
(3) the LiCuLaZrMO powder tabletting in step (2) is obtained into LiCuLaZrMO piece with tablet press machine, in calcination vessel
The LiCuLaZrMO piece is inserted into LiCuLaZrMO powder, at 1000~1159 DEG C by middle addition LiCuLaZrMO powder
Sintering, is cooled to room temperature, obtains the LiCuLaZrMO solid electrolyte.
Need in the prior art 1600 DEG C of high temperature maturing temperature and higher presoma treatment temperature, be to obtain
Preferably, satisfactory compact texture.The present invention is added to the Cu elemental dopant that can make ceramic dense, and lithium salts uses energy
The lithium salts for forming low lowest total of the melting point, using the characteristic of Cu element, so that each element forms fine and close knot in LiCuLaZrMO
Structure, so that presoma calcination process obtains temperature and is reduced to 300~809 DEG C, and in the prior art, presoma calcination process then needs
810~990 DEG C, preliminary satisfactory compact texture could be formed；And subsequent maturing temperature of the invention is greatly reduced.
Also, on the basis of LiCuLaZrO, M compound is further added, due to the association of Cu compound and M compound
The conductivity of electrolyte can be improved with effect.
The additive amount of preferred Cu element and M element will lead to impurity when the additive amount of Cu element is excessive in the present invention
It generates, reduces the consistency of LiCuLaZrMO, when the additive amount of Cu element is very few, Cu is caused to improve the consistency of LiCuLaZrMO
Effect it is not significant；Will lead to by the generation of impurity, reduce LiCuLaZrMO's when M element additive amount is excessive for M element
Consistency, when the additive amount of M element is very few, the effect for improving the consistency of LiCuLaZrMO is not significant；The present invention passes through excellent
Change the doping of Cu and M element, collaboration improves the consistency of LiCuLaZrMO solid electrolyte, to obtain preferably conductive
Effect.
In step (1), the La2O3、ZrO2, copper compound, M compound and lithium salts molar ratio be 1.25~1.50:
1.60~2.00:0.10~3.00:0.01~0.67:7.15~9.80.
Preferably, in step (1), the La2O3、ZrO2, copper compound, M compound and lithium salts molar ratio are as follows: 1.25
~1.50:1.60~2.00:0.10~1.50:0.01~0.67:7.15~9.80.
The present invention can further decrease the treatment temperature of sample by the content of further preferred Cu element.
In step (1), the M compound is selected from strontium compound, barium compound, calcium compound, tungsten oxide or rare earth oxygen
One or more of compound.
In step (1), the strontium compound is selected from strontium carbonate, strontium sulfate, strontium chloride, strontium nitrate, strontium acetate or hydroxide
One or more of strontium；The barium compound is selected from barium sulfate, barium carbonate, barium chloride, barium nitrate, barium acetate or barium hydroxide
One or more of；The calcium compound is selected from calcium oxide, calcium carbonate, calcium sulfate, calcium chloride, calcium nitrate, calcium acetate or hydrogen
One or more of calcium oxide；The rare earth oxide is selected from cerium oxide, praseodymium oxide, neodymium oxides, samarium oxide, europium
Oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmia, Er oxide, thulium oxide, ytterbium oxide, lutetium oxidation
The one or more given in object, scandium oxide or yttrium oxide.
In step (1), the copper compound is selected from copper sulphate, Kocide SD, copper nitrate, copper chloride, copper carbonate or oxidation
One or more of copper.
In step (1), the lithium salts is in lithium hydroxide, lithium nitrate, lithium chloride, lithium oxalate, lithia, lithium carbonate
It is one or more of.
In step (1), the dispersing agent is selected from one or more of ethylene glycol, propyl alcohol or isopropanol.
In step (2), the calcining time of presoma is 5~7h.
In step (3), the method for the LiCuLaZrMO piece insertion LiCuLaZrMO powder are as follows: in calcination vessel, from
One layer of LiCuLaZrMO powder, one layer of LiCuLaZrMO piece and one layer and LiCuLaZrMO powder are successively laid under upper；
The ratio of the LiCuLaZrMO powder total weight and the LiCuLaZrMO piece total weight is 0.2~1.
In step (3), the sintering time of the LiCuLaZrMO piece and LiCuLaZrMO powder is 5~12h.
Compared with prior art, the invention has the following advantages that
(1) synthesis temperature of the invention for preparing LiCuLaZrMO solid electrolyte is lower, the roasting of presoma calcination process
Temperature is only 300~809 DEG C, and sintering temperature is only 1000~1159 DEG C, reduces the requirement to roasting apparatus；
(2) due to reducing the maturing temperature and sintering temperature of presoma calcination process, the energy is saved；
(3) lithium ion conductivity of LiCuLaZrMO solid electrolyte prepared by the present invention is 7.63 × 10-4S·cm-1~
9.92×10-3S·cm-1, conduct electricity very well.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Present embodiments provide a kind of LiCuLaZrMO method for preparing solid electrolyte, step are as follows:
(1) La is weighed respectively2O3、ZrO2, copper compound, M compound and lithium salts in ball grinder, be added a certain amount of point
Powder, 2~9h of ball milling is dry, obtains presoma；Wherein copper compound is copper sulphate, Kocide SD, copper nitrate, copper chloride, carbon
One of sour copper, copper oxide or more than one mixture；M compound be strontium compound (strontium carbonate, strontium sulfate, strontium chloride,
Strontium nitrate, strontium acetate, strontium hydroxide), barium compound (barium sulfate, barium carbonate, barium chloride, barium nitrate, barium acetate, hydroxide
Barium), it is calcium compound (calcium oxide, calcium carbonate, calcium sulfate, calcium chloride, calcium nitrate, calcium acetate, calcium hydroxide), tungsten oxide, dilute
One of native oxide (cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium oxide) or it is a kind of with
On mixture；Lithium salts be one of lithium hydroxide, lithium nitrate, lithium chloride, lithium oxalate, lithia, lithium carbonate or it is a kind of with
On mixture；Wherein La2O3:ZrO2: copper compound: M compound: lithium salts (molar ratio) be 1.25~1.50:1.60~
2.00:0.10~1.50:0.01~0.67:7.15~9.80；Dispersing agent is one of ethylene glycol, propyl alcohol, isopropanol or one
Kind or more mixture.
(2) above-mentioned presoma is put into crucible, 5~7h of calcination, is cooled to room temperature at 300~809 DEG C, grinds, and obtains
LiCuLaZrMO powder；
(3) above-mentioned LiCuLaZrMO powder is pressed into piece with tablet press machine and obtains LiCuLaZrMO piece, be added in crucible
LiCuLaZrMO piece is inserted into LiCuLaZrMO powder by LiCuLaZrMO powder, and 5~12h is sintered at 1000~1159 DEG C,
It is cooled to room temperature, obtains LiCuLaZrMO solid electrolyte.
LiCuLaZrMO solid electrolyte lithium ion conductivity Britain obtained in various embodiments of the present invention
Solartron1260+1287 electrochemical workstation is measured, and measuring method is shown in Solartron1260+1287 electrochemical operation
The operation instructions stood.
LiCuLaZrMO solid electrolyte is prepared using specific embodiment below, and carries out electro conductivity performance measurement.
Embodiment 1
Weigh 1.25 moles of La2O3, 1.60 moles of ZrO2, 0.10 mol sulfuric acid copper, 0.01 mole of strontium carbonate, 2.75 moles
Lithium hydroxide and 4.43 molar nitric acid lithiums are respectively that a certain amount of ethylene glycol is added in 5L ball grinder, and ball milling 2h is dry, obtains
To presoma.Above-mentioned presoma is put into 3L crucible, calcination 5h, is cooled to room temperature at 300 DEG C, grinds, and obtains
LiCuLaZrSrO powder.Above-mentioned LiCuLaZrSrO powder is pressed into piece with tablet press machine and obtains LiCuLaZrSrO piece, in crucible
LiCuLaZrSrO powder is added, LiCuLaZrSrO piece is inserted into LiCuLaZrSrO powder, 5h is sintered at 1000 DEG C, it is cold
To room temperature, LiCuLaZrSrO solid electrolyte is obtained.The lithium ion conductivity of obtained LiCuLaZrSrO solid electrolyte is
7.63×10-4S·cm-1。
Embodiment 2
Weigh 1.50 moles of La2O3, 2.00 moles of ZrO2, 1.00 moles copper, 0.50 mole of Kocide SD, 0.03 rubs
That calcium oxide, 0.45 mole of WO3, 0.19 mole of Y2O3It is respectively to be added a certain amount of in 5L ball grinder with 9.80 moles of lithium carbonates
Isopropanol, ball milling 9h is dry, obtains presoma.Above-mentioned presoma is put into 3L crucible, calcination 7h, is cooled at 809 DEG C
Room temperature is ground, and obtains LiCuLaZrCaWYO powder.Above-mentioned LiCuLaZrCaWYO powder piece is pressed into tablet press machine to obtain
LiCuLaZrCaWYO powder is added in crucible, LiCuLaZrCaWYO piece is inserted into for LiCuLaZrCaWYO piece
In LiCuLaZrCaWYO powder, it is sintered 12h at 1159 DEG C, is cooled to room temperature, obtains LiCuLaZrCaWYO solid electrolyte.?
The lithium ion conductivity of the LiCuLaZrCaWYO solid electrolyte arrived is 5.23 × 10-3S·cm-1。
Embodiment 3
Weigh 1.38 moles of La2O3, 1.80 moles of ZrO2, 0.20 molar nitric acid copper, 0.30 mole of copper chloride, 0.30 mole
Copper carbonate, 0.02 mol sulfuric acid barium, 0.32 mole of WO3, 6.28 moles of lithium carbonates and 2.20 molar lithium hydroxides be respectively in 5L
In ball grinder, a certain amount of propyl alcohol is added, ball milling 5.5h is dry, obtains presoma.Above-mentioned presoma is put into 3L crucible,
Calcination 6h, is cooled to room temperature at 554 DEG C, grinds, and obtains LiCuLaZrBaWO powder.With tablet press machine by above-mentioned LiCuLaZrBaWO
Powder is pressed into piece and obtains LiCuLaZrBaWO piece, and LiCuLaZrBaWO powder is added in crucible, LiCuLaZrBaWO piece is inserted
Enter in LiCuLaZrBaWO powder, be sintered 8.5h at 1079 DEG C, be cooled to room temperature, obtains LiCuLaZrBaWO solid electrolyte.?
The lithium ion conductivity of the LiCuLaZrCaWYO solid electrolyte arrived is 9.92 × 10-3S·cm-1。
Embodiment 4
Weigh 1.32 moles of La2O3, 1.70 moles of ZrO2, 0.20 mole of Kocide SD, 0.25 molar nitric acid copper, 0.01 rub
That strontium nitrate, 0.02 mole of barium hydroxide, 0.145 mole of Y2O3, 4.93 moles of lithium chlorides and 2.90 molar lithium hydroxides be respectively
In 5L ball grinder, a certain amount of propyl alcohol is added, ball milling 3.8h is dry, obtains presoma.Above-mentioned presoma is put into 3L crucible
In, calcination 5.5h, is cooled to room temperature at 427 DEG C, grinds, and obtains LiCuLaZrSrBaYO powder.It will be above-mentioned with tablet press machine
LiCuLaZrSrBaYO powder is pressed into piece and obtains LiCuLaZrSrBaYO piece, and LiCuLaZrSrBaYO powder is added in crucible,
LiCuLaZrSrBaYO piece is inserted into LiCuLaZrSrBaYO powder, 7h is sintered at 1040 DEG C, is cooled to room temperature, obtain
LiCuLaZrSrBaYO solid electrolyte.The lithium ion conductivity of obtained LiCuLaZrSrBaYO solid electrolyte be 9.68 ×
10-3S·cm-1。
Embodiment 5
Weigh 1.44 moles of La2O3, 1.90 moles of ZrO2, 1.15 moles copper, 0.31 mole of Gd2O3, 0.20 mole
Sm2O3, 6.75 molar lithium hydroxides, 2.37 moles of lithium carbonates, 0.01 molar oxalic acid lithium and 0.01 moles lithium be respectively in 5L
In ball grinder, a certain amount of propyl alcohol is added, ball milling 7.3h is dry, obtains presoma.Above-mentioned presoma is put into 3L crucible,
Calcination 6.5h, is cooled to room temperature at 682 DEG C, grinds, and obtains LiCuLaZrGdSmO powder.It will be above-mentioned with tablet press machine
LiCuLaZrGdSmO powder is pressed into piece and obtains LiCuLaZrGdSmO piece, and LiCuLaZrGdSmO powder is added in crucible, will
LiCuLaZrGdSmO piece is inserted into LiCuLaZrGdSmO powder, is sintered 10.3h at 1119 DEG C, is cooled to room temperature, obtains
LiCuLaZrGdSmO solid electrolyte.The lithium ion conductivity of obtained LiCuLaZrGdSmO solid electrolyte be 8.97 ×
10-3S·cm-1。
Embodiment 6
Weigh 1.50 moles of La2O3, 2.00 moles of ZrO2, 2.00 moles copper, 1.00 moles of Kocide SDs, 0.03 rub
That calcium oxide, 0.45 mole of WO3,0.19 mole of Y2O3It is respectively to be added a certain amount of in 5L ball grinder with 9.80 moles of lithium carbonates
Isopropanol, ball milling 9h is dry, obtains presoma.Above-mentioned presoma is put into 3L crucible, calcination 7h, is cooled at 900 DEG C
Room temperature is ground, and obtains LiCuLaZrCaWYO powder.Above-mentioned LiCuLaZrCaWYO powder piece is pressed into tablet press machine to obtain
LiCuLaZrCaWYO powder is added in crucible, LiCuLaZrCaWYO piece is inserted into for LiCuLaZrCaWYO piece
In LiCuLaZrCaWYO powder, it is sintered 12h at 1170 DEG C, is cooled to room temperature, obtains LiCuLaZrCaWYO solid electrolyte.?
The lithium ion conductivity of the LiCuLaZrCaWYO solid electrolyte arrived is 8.53 × 10-4S·cm-1。
By comparing the solid electrolyte of Examples 1 to 6 and documents, it can be seen that the electrolyte in the present embodiment
Pretreatment temperature and maturing temperature it is lower, and obtain solid electrolyte lithium ion conductivity and documents in
Lithium ion conductivity it is suitable, therefore, from the heatproof degree and preparation process to Preparation equipment power conservation requirement angle come
It says, the solid electrolyte in the present embodiment has apparent advantage.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of LiCuLaZrMO method for preparing solid electrolyte, which comprises the following steps:
(1) by La2O3、ZrO2, copper compound, M compound and lithium salts mixing, be added dispersing agent, before grinding, being dried to obtain
Drive body；
(2) presoma in step (1) is cooled to room temperature, ground in 300~809 DEG C of calcination process, obtain LiCuLaZrMO powder
Body；
(3) the LiCuLaZrMO powder tabletting in step (2) is obtained into LiCuLaZrMO piece with tablet press machine, added in calcination vessel
Enter LiCuLaZrMO powder, the LiCuLaZrMO piece be inserted into LiCuLaZrMO powder, is sintered at 1000~1159 DEG C,
It is cooled to room temperature, obtains the LiCuLaZrMO solid electrolyte.
2. a kind of LiCuLaZrMO method for preparing solid electrolyte according to claim 1, which is characterized in that step
(1) in, the La2O3、ZrO2, copper compound, M compound and lithium salts molar ratio be 1.25~1.50:1.60~2.00:
0.10~3.00:0.01~0.67:7.15~9.80.
3. a kind of LiCuLaZrMO method for preparing solid electrolyte according to claim 2, which is characterized in that step
(1) in, the La2O3、ZrO2, copper compound, M compound and lithium salts molar ratio are as follows: 1.25~1.50:1.60~
2.00:0.10~1.50:0.01~0.67:7.15~9.80.
4. a kind of LiCuLaZrMO method for preparing solid electrolyte according to claim 1, which is characterized in that step
(1) in, the M compound is selected from one of strontium compound, barium compound, calcium compound, tungsten oxide or rare earth oxide
Or it is several；The strontium compound be selected from one of strontium carbonate, strontium sulfate, strontium chloride, strontium nitrate, strontium acetate or strontium hydroxide or
It is several；The barium compound is selected from one of barium sulfate, barium carbonate, barium chloride, barium nitrate, barium acetate or barium hydroxide or several
Kind；The calcium compound in calcium oxide, calcium carbonate, calcium sulfate, calcium chloride, calcium nitrate, calcium acetate or calcium hydroxide one
Kind is several；The rare earth oxide is selected from cerium oxide, praseodymium oxide, neodymium oxides, samarium oxide, europium oxide, gadolinium oxygen
Compound, terbium oxide, dysprosium oxide, holmia, Er oxide, thulium oxide, ytterbium oxide, lutetium oxide, scandium oxide
Or the one or more given in yttrium oxide.
5. a kind of LiCuLaZrMO method for preparing solid electrolyte according to claim 1, which is characterized in that step
(1) in, the copper compound be selected from one of copper sulphate, Kocide SD, copper nitrate, copper chloride, copper carbonate or copper oxide or
It is several.
6. a kind of LiCuLaZrMO method for preparing solid electrolyte according to claim 1, which is characterized in that step
(1) in, the lithium salts is selected from one or more of lithium hydroxide, lithium nitrate, lithium chloride, lithium oxalate, lithia, lithium carbonate.
7. a kind of LiCuLaZrMO method for preparing solid electrolyte according to claim 1, which is characterized in that step
(1) in, the dispersing agent is selected from one or more of ethylene glycol, propyl alcohol or isopropanol.
8. a kind of LiCuLaZrMO method for preparing solid electrolyte according to claim 1, which is characterized in that step
(2) in, the calcining time of presoma is 5~7h.
9. a kind of LiCuLaZrMO method for preparing solid electrolyte according to claim 1, which is characterized in that step
(3) in, the method for LiCuLaZrMO piece insertion LiCuLaZrMO powder are as follows: in calcination vessel, successively spread under upper
If one layer of LiCuLaZrMO powder, one layer of LiCuLaZrMO piece and one layer and LiCuLaZrMO powder；It is described
The ratio of LiCuLaZrMO powder total weight and the LiCuLaZrMO piece total weight is 0.2~1；The LiCuLaZrMO piece and
The sintering time of LiCuLaZrMO powder is 5~12h.
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