CN108946807A - A kind of solid electrolyte Li7La3Zr2O12Raw powder's production technology - Google Patents
A kind of solid electrolyte Li7La3Zr2O12Raw powder's production technology Download PDFInfo
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Abstract
The invention discloses a kind of solid electrolyte Li7La3Zr2O12Raw powder's production technology, comprising the following steps: 1) press chemical formula Li7La3Zr2O12In elemental mole ratios weigh Li source compound, lanthanum source compound and zirconium source compound respectively, Li source compound and lanthanum source compound are dissolved in organic solvent, solution A is obtained；Zirconium source compound is dissolved in organic solvent, and is added dropwise to chelating agent in whipping process, obtains solution B；2) solution A is mixed with solution B, obtains Li7La3Zr2O12Wet gel；3) wet gel obtains Li through drying7La3Zr2O12Xerogel；4) xerogel is put into cooling after being pre-sintered in agglomerating plant and obtains Li7La3Zr2O12Precursor powder；5) precursor powder being prepared is subjected to Fast Sintering under inert gas protection, is cooled to room temperature to obtain Li7La3Zr2O12Powder.The advantages of present invention incorporates sol-gal process and Fast Sintering methods, obtained powder purity height, better crystallinity degree, particle diameter distribution are uniform, while reducing sintering temperature, also shorten manufacturing cycle.
Description
[technical field]
The present invention relates to solid electrolyte more particularly to a kind of solid electrolyte Li7La3Zr2O12Raw powder's production technology.
[background technique]
Lithium ion battery has attracted attention always since putting goods on the market since 1991, in mobile phone, laptop, automobile, electricity
The field of batteries such as dynamic bicycle are widely used.The electrolyte building block indispensable as lithium ion battery, its performance exist
Largely influence the performance indexes of battery.What commercial li-ion battery generallyd use at present is liquid electrolyte, liquid
State electrolyte although lithium ion conductivity with higher, but its easily leakage, perishable, the labile feature of high temperature make its presence
The security risks such as spontaneous combustion or explosion, while it is also easy to react with electrode and generates Li dendrite.Therefore, using solid electrolyte
Instead of traditional electrolyte, Development of Novel all-solid lithium-ion battery is to solve the problems, such as cell safety, improve battery energy storage density
New technology thinking (Kamaya N, Homma K, Yamakawa Y, et al.Nature Materials, 2011,10 (9): 682-
6)。
Inorganic solid electrolyte is due to it has the characteristics that security performance is high, energy density is big by the parent of researchers
It looks at.Wherein garnet-type solid electrolyte Li7La3Zr2O12(LLZO) ionic conductivity with higher contacts surely with lithium metal
It is fixed, while also there is excellent stability and chemical property, electrochemical window is up to 6V, this expands positive and negative pole material
Range of choice provides possibility for exploitation high-capacity lithium battery, these advantages make it in following all-solid lithium-ion battery, lithium
The fields such as air cell have broad application prospects.
The method for preparing LLZO has conventional solid reaction method, sol-gal process and field to help sintering process etc..Using conventional solid
When reaction method prepares LLZO, preparation process is complex and time-consuming, and precursor needs to first pass through pre-burning, tabletting, then in height
The lower prolonged heat preservation of temperature be sintered (R.Murugan, V.Thangadurai and W.Weppner.Chem.Int.Ed.,
2007,46:7778-7781).Due to keeping the temperature for a long time, it is be easy to cause the volatilization of elemental lithium, to be unable to control containing for lithium
Amount, and La easily generated in sintering process2Zr2O7And La2O3Miscellaneous phase, the generation of these miscellaneous phases can deteriorate the electrochemistry of material
Energy.Sol-gal process is also one of more common method, and sol-gal process can be such that each component is uniformly mixed in the liquid phase, mutually
Reaction, obtains evengranular precursor powder, then sintering can prepare nano-scale lattice at relatively low temperature
LLZO powder (Sakamoto J, Rangasamy E, Kim H, et al.Nanotechno logy, 2013,24 (42):
3532-3540), this has benifit, but only drawback is that sintering for the preparation of composite solid electrolyte and performance optimization very much
Time is still up to 10h.Field helps the Fast Sintering for being sintered and material can be achieved, and can reduce the loss of elemental lithium at high temperature, such as
(Zhang Y, Chen F, Rong T, et al.Journal of Power Sources, 2014,268 (3): 960-such as Zhang
964) LLZO is prepared under the conditions of 1100 DEG C of sintering temperatures using Fast Sintering technology, sintering time is only 10mi n, but phase
It is higher than its sintering temperature in sol-gal process.
To solve the problems such as sintering temperature existing for existing LLZO technology of preparing is high, sintering time is long, process is cumbersome, need
A kind of efficient, energy-efficient preparation method, can be shortened manufacturing cycle while reducing sintering temperature, final to obtain purity is high, knot
Brilliant degree is good, the LLZO solid electrolyte material of even particle size distribution.
[summary of the invention]
The technical problem to be solved in the present invention is to provide one kind can reduce sintering temperature, shortens manufacturing cycle, and powder is pure
Degree is high, better crystallinity degree, the solid electrolyte Li of even particle size distribution7La3Zr2O12Raw powder's production technology.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that, a kind of solid electrolyte Li7La3Zr2O12
Raw powder's production technology, comprising the following steps:
101) chemical formula Li is pressed7La3Zr2O12In elemental mole ratios weigh Li source compound, lanthanum source compound and zirconium respectively
Li source compound and lanthanum source compound are dissolved in organic solvent, obtain solution A by source compound；Zirconium source compound, which is dissolved in, to be had
In solvent, and it is added dropwise to chelating agent in whipping process, obtains solution B；
102) solution A is mixed with solution B, obtains Li7La3Zr2O12Wet gel；
103) wet gel obtains Li through drying7La3Zr2O12Xerogel；
104) xerogel is put into cooling after being pre-sintered in agglomerating plant and obtains Li7La3Zr2O12Precursor powder；
105) precursor powder being prepared is subjected to Fast Sintering under inert gas protection, is cooled to room temperature to obtain
Li7La3Zr2O12Powder.
Above-described preparation method, the Fast Sintering in step 105 are that microwave sintering, plasma activated sintering or field help
Sintering.
Above-described preparation method, the Li source compound are one of lithium carbonate, lithium nitrate and lithium acetate, lanthanum
Source compound is one of lanthana, lanthanum acetate and lanthanum nitrate, and zirconium source compound is zirconium oxychloride, zirconyl nitrate, ethyl alcohol
One of zirconium and propyl alcohol zirconium；Organic solvent is in methanol, ethyl alcohol, propyl alcohol, ethylene glycol, butanol, ethylene oxide and dimethylbenzene
At least one, chelating agent are at least one of hydrochloric acid, acetic acid, boric acid, sulfuric acid, phosphoric acid and ammonium hydroxide.
Above-described preparation method, in solution A, the sum of amount of substance of Li source compound and lanthanum source compound with it is organic
The ratio between volume of solvent is 1mmol:2ml~1mmol:20ml.
Above-described preparation method, the ratio between the amount of substance and the volume of organic solvent of zirconium source compound are in solution B
The mass ratio of 1mmol:1ml~1mmol:8ml, zirconium source compound and chelating agent is 1:1~1:6.
Xerogel is placed in crucible by above-described preparation method in step 104), is put into pre-burning in agglomerating plant
Cooling obtains Li after knot7La3Zr2O12Precursor powder；The crucible is oxidation zirconium crucible, alumina crucible or lanthana earthenware
Crucible.
Above-described preparation method, the agglomerating plant in step 104) are Muffle furnace, tube furnace, van-type furnace or vacuum
Furnace.
Above-described preparation method, the pre-sintering process in step 104) are as follows: heating rate be 2 DEG C/min~20 DEG C/
Min, sintering temperature is 300 DEG C~500 DEG C, soaking time is 2h~3h.
Above-described preparation method, the inert gas in step 105) are at least one of argon gas, helium and nitrogen.
Above-described preparation method, the Fast Sintering technique in step 105) are as follows: heating rate is 50~200 DEG C/
Min, sintering temperature is 900 DEG C~1100 DEG C, soaking time is 1~30min.
Solid electrolyte Li of the present invention7La3Zr2O12Raw powder's production technology combines sol-gal process and Fast Sintering method
The advantages of, obtained powder purity height, better crystallinity degree, particle diameter distribution are uniform, while reducing sintering temperature, also shorten
Manufacturing cycle.
[Detailed description of the invention]
Fig. 1 is the process flow chart of the embodiment of the present invention.
Fig. 2 is Li of the embodiment of the present invention7La3Zr2O12X-ray diffractogram of system at a temperature of different Fast Sinterings.
Fig. 3 obtains Li in 1000 DEG C of sintering for the embodiment of the present invention7La3Zr2O12The microscopic appearance figure of powder.
[specific embodiment]
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and however, it is not limited to this,
It is all technical solution of the present invention simply to be modified or equivalent replacement, it should all be included within the scope of protection of the present invention.
Solid electrolyte Li provided by the invention7La3Zr2O12Raw powder's production technology, be it is a kind of using sol-gal process and
Fast Sintering method, which is combined, prepares solid electrolyte Li7La3Zr2O12The method of powder, method includes the following steps:
(1) chemical formula Li is pressed7La3Zr2O12Middle elemental mole ratios weigh Li source compound, lanthanum source compound respectively, and being dissolved in has
In solvent, solution A is obtained by revolving speed stirring 0.5h~4h of 100r/min~600r/min at room temperature；By elemental mole ratios
Zirconium source compound is measured, is dissolved in organic solvent, adds dropwise during stirring by 10 drops/min~40 drops/min speed
Enter chelating agent, obtains solution B by revolving speed stirring 0.5h~4h of 100r/min~600r/min；
(2) solution A is added completely into solution B, 1h~10h is stirred at 20 DEG C~80 DEG C, then at 20 DEG C~80 DEG C
Lower standing 1h~15h obtains Li7La3Zr2O12Wet gel；
(3) wet gel obtains Li through dry 4h~48h7La3Zr2O12Xerogel；
(4) xerogel is placed in crucible, is put into cooling after being pre-sintered in agglomerating plant and obtains Li7La3Zr2O12Presoma
Powder；
(5) precursor powder being prepared is placed in mold, carries out Fast Sintering under inert gas protection, it is cooling
Li is obtained to room temperature7La3Zr2O12Powder.
Wherein, flash sintering method can help sintering for microwave sintering, plasma activated sintering or field.
Li source compound is one of lithium carbonate, lithium nitrate and lithium acetate, lanthanum source compound be lanthana, lanthanum acetate and
One of lanthanum nitrate, zirconium source compound are one of zirconium oxychloride, zirconyl nitrate, ethyl alcohol zirconium and propyl alcohol zirconium, You Jirong
Agent is a variety of, the chelating of one of methanol, ethyl alcohol, propyl alcohol, ethylene glycol, butanol, ethylene oxide and dimethylbenzene or arbitrary proportion
Agent is a variety of of one of hydrochloric acid, acetic acid, boric acid, sulfuric acid, phosphoric acid and ammonium hydroxide or arbitrary proportion.
The ratio between the sum of amount of substance of Li source compound and lanthanum source compound and the volume of organic solvent are in solution A
1mmol:(2ml~20ml).
The ratio between the amount of the substance of zirconium source compound and the volume of organic solvent are 1mmol:(1ml~8ml in solution B), zirconium
The ratio between amount of substance of source compound and chelating agent is 1:(1~6).
Crucible is zirconium oxide, aluminium oxide or lanthana crucible.
Agglomerating plant is Muffle furnace, tube furnace, van-type furnace or vacuum drying oven.
Pre-sintering process are as follows: heating rate is 2 DEG C/min~20 DEG C/min, and sintering temperature is 300 DEG C~500 DEG C, keeps the temperature
Time is 2h~3h.
Inert gas is a variety of of one of argon gas, helium and nitrogen or arbitrary proportion.
Fast Sintering technique are as follows: heating rate is 50~200 DEG C/min, when sintering temperature is 900 DEG C~1100 DEG C, keeps the temperature
Between be 1~30min.
Embodiment 1:
By chemical formula Li7La3Zr2O12Middle elemental mole ratios weigh 3.103g lithium carbonate and 5.865g lanthana respectively, are dissolved in
In the ethyl alcohol of 50ml, solution A is obtained by the revolving speed stirring 30min of 400r/min at room temperature；The ethyl alcohol zirconium of 3.257g is measured again,
It is dissolved in the ethyl alcohol of 50ml, the hydrochloric acid of 0.965ml is added dropwise by 20 drops/min speed during stirring, at room temperature
Solution B is obtained by the revolving speed stirring 30min of 400r/min；Solution A is added completely into solution B, continues to stir under 3h, then room temperature
Stand 12h；By wet gel by dry 12h, Li is obtained7La3Zr2O12Xerogel；Xerogel is placed in alumina crucible, is put
Enter Muffle furnace, rises to 450 DEG C by 5 DEG C/min heating rate, furnace cooling obtains Li after keeping the temperature 3h7La3Zr2O12Precursor powder；
It weighs 3g precursor powder to be placed in mold, is put into the plasma activated sintering equipment full of argon gas and carries out Fast Sintering, press
80 DEG C/min heating rate rises to 950 DEG C from room temperature, is cooled to room temperature after keeping the temperature 3min, and gained powder is the embodiment of the present invention 1
Solid electrolyte Li7La3Zr2O12。
Embodiment 2:
By chemical formula Li7La3Zr2O12Middle elemental mole ratios weigh 2.896g lithium nitrate and 7.794g lanthanum nitrate respectively, are dissolved in
In the ethylene glycol of 45ml, solution A is obtained by the revolving speed stirring 40min of 300r/min at room temperature；2.775g Nitric Acid Oxidation is measured again
Zirconium is dissolved in the ethylene glycol of 45ml, and the nitric acid of 1.054ml is added dropwise by 20 drops/min speed during stirring,
Solution B is obtained by the revolving speed stirring 40min of 300r/min at room temperature；Solution A is added completely into solution B, continues to stir 4h, then
6h is stood under room temperature；For 24 hours by drying by wet gel, Li is obtained7La3Zr2O12Xerogel；Xerogel is placed in alumina crucible
In, it is put into Muffle furnace, rises to 450 DEG C by 5 DEG C/min heating rate, furnace cooling obtains Li after keeping the temperature 3h7La3Zr2O12Presoma
Powder；It weighs 3g precursor powder to be placed in mold, is put into the plasma activated sintering equipment full of argon gas and is quickly burnt
Knot rises to 1000 DEG C from room temperature by 80 DEG C/min heating rate, is cooled to room temperature after keeping the temperature 5min, and gained powder is that the present invention is real
Apply the solid electrolyte Li of example 27La3Zr2O12。
Embodiment 3:
By chemical formula Li7La3Zr2O12Middle elemental mole ratios weigh 2.896g lithium nitrate and 7.794g lanthanum nitrate respectively, are dissolved in
In the normal propyl alcohol of 45ml, solution A is obtained by the revolving speed stirring 40min of 300r/min at room temperature；The propyl alcohol of 5.308ml is measured again
Zirconium is dissolved in the normal propyl alcohol of 45ml, and the glacial acetic acid of 1.029ml is added dropwise by 20 drops/min speed during stirring,
Solution B is obtained by the revolving speed stirring 40min of 300r/min at room temperature；Solution A is added completely into solution B, continues to stir 4h,
6h is stood under room temperature again；For 24 hours by drying by wet gel, Li is obtained7La3Zr2O12Xerogel；Xerogel is placed in aluminium oxide earthenware
In crucible, it is put into Muffle furnace, rises to 450 DEG C by 5 DEG C/min heating rate, furnace cooling obtains Li after keeping the temperature 3h7La3Zr2O12Forerunner
Body powder；It weighs 3g precursor powder to be placed in mold, is put into the discharging plasma sintering equipment full of argon gas and carries out quickly
Sintering rises to 1050 DEG C from room temperature by 80 DEG C/min heating rate, is cooled to room temperature after keeping the temperature 8min, and gained powder is the present invention
The solid electrolyte Li of embodiment 37La3Zr2O12。
Embodiment 4:
By chemical formula Li7La3Zr2O12Middle elemental mole ratios weigh 2.896g lithium nitrate and 7.794g lanthanum nitrate respectively, are dissolved in
In the normal propyl alcohol of 45ml, solution A is obtained by the revolving speed stirring 40min of 300r/min at room temperature；2.137g dichloro oxygen is measured again
Change zirconium, be dissolved in the normal propyl alcohol of 45ml, the hydrochloric acid of 0.965ml is added dropwise by 20 drops/min speed during stirring,
Solution B is obtained by the revolving speed stirring 30min of 600r/min at room temperature；Solution A is added completely into solution B, continues to stir 4h,
6h is stood under room temperature again；For 24 hours by drying by wet gel, Li is obtained7La3Zr2O12Xerogel；Xerogel is placed in aluminium oxide earthenware
In crucible, it is put into tube furnace, rises to 400 DEG C by 5 DEG C/min heating rate, furnace cooling obtains Li after keeping the temperature 2h7La3Zr2O12Forerunner
Body powder；It weighs 3g precursor powder to be placed in mold, is put into the discharging plasma sintering equipment full of argon gas and carries out quickly
Sintering rises to 1000 DEG C from room temperature by 80 DEG C/min heating rate, is cooled to room temperature after keeping the temperature 10min, and gained powder is this hair
The solid electrolyte Li of bright embodiment 47La3Zr2O12。
Embodiment 5:
By chemical formula Li7La3Zr2O12Middle elemental mole ratios weigh 3.103g lithium carbonate and 5.865g lanthana respectively, are dissolved in
In the ethyl alcohol of 60ml, solution A is obtained by the revolving speed stirring 30min of 400r/min at room temperature；The Nitric Acid Oxidation of 2.775g is measured again
Zirconium is dissolved in the ethyl alcohol of 60ml, the nitric acid of 0.965ml is added dropwise by 20 drops/min speed during stirring, in room
Solution B is obtained by the revolving speed stirring 30min of 400r/min under temperature；Solution A is added completely into solution B, continues to stir 3h, then often
Temperature is lower to stand 12h；By wet gel by dry 12h, Li is obtained7La3Zr2O12Xerogel；Xerogel is placed in alumina crucible
In, it is put into tube furnace, rises to 400 DEG C by 5 DEG C/min heating rate, furnace cooling obtains Li after keeping the temperature 3h7La3Zr2O12Presoma
Powder；It weighs 3g precursor powder to be placed in mold, is put into the microwave agglomerating furnace full of nitrogen and carries out Fast Sintering, by 80
DEG C/min heating rate from room temperature rises to 950 DEG C, it is cooled to room temperature after keeping the temperature 5min, gained powder is the embodiment of the present invention 5
Solid electrolyte Li7La3Zr2O12。
Embodiment 6:
By chemical formula Li7La3Zr2O12Middle elemental mole ratios weigh 2.772g lithium acetate and 5.689g lanthanum acetate respectively, are dissolved in
In the normal propyl alcohol of 45ml, solution A is obtained by the revolving speed stirring 40min of 300r/min at room temperature；The propyl alcohol of 5.308ml is measured again
Zirconium is dissolved in the normal propyl alcohol of 45ml, and the glacial acetic acid of 1.029ml is added dropwise by 20 drops/min speed during stirring,
Solution B is obtained by the revolving speed stirring 40min of 300r/min at room temperature；Solution A is added completely into solution B, continues to stir 4h,
6h is stood under room temperature again；For 24 hours by drying by wet gel, Li is obtained7La3Zr2O12Xerogel；Xerogel is placed in aluminium oxide earthenware
In crucible, it is put into Muffle furnace, rises to 450 DEG C by 5 DEG C/min heating rate, furnace cooling obtains Li after keeping the temperature 3h7La3Zr2O12Forerunner
Body powder；It weighs 3g precursor powder to be placed in mold, is put into the discharging plasma sintering equipment full of argon gas and carries out quickly
Sintering rises to 1100 DEG C from room temperature by 80 DEG C/min heating rate, is cooled to room temperature after keeping the temperature 3min, and gained powder is the present invention
The solid electrolyte Li of embodiment 67La3Zr2O12。
The Li that each embodiment is prepared7La3Zr2O12Powder carries out X-ray diffraction analysis, to determine its object phase composition
And crystal structure, as shown in Figure 2.It can be seen that Fast Sintering in 950~1100 DEG C of temperature from the XRD characteristic diffraction peak of sample
Available object compares pure Li in range7La3Zr2O12Powder.
To obtained Li7La3Zr2O12Sample is scanned Electronic Speculum test, obtains its microscopic appearance such as Fig. 3.It can be with from Fig. 3
Find out the Li obtained after sintering7La3Zr2O12Powder crystallinity is fine, even particle size distribution.
Above embodiments of the present invention have the advantage that compared with prior art
One, presoma powder is prepared using sol-gal process, the powder purity that is sintered is high, better crystallinity degree, granularity point
Cloth is uniform.
Two, the sintering time of Fast Sintering only needs more than ten minutes, reduces the loss of Li；Meanwhile it can be largely
The time for shortening high temperature sintering, shorten manufacturing cycle.
Three, sol-gal process and Fast Sintering can reduce the sintering temperature of product, and cubic phase can be obtained at 900 DEG C
Li7La3Zr2O12, 330 DEG C are reduced compared with needed for conventional solid sintering 1230 DEG C.
Four, required sintering temperature is low, and sintering time is short, for producing in enormous quantities, can reduce energy consumption, be effectively reduced
Preparation cost.
Claims (10)
1. a kind of solid electrolyte Li7La3Zr2O12Raw powder's production technology, which comprises the following steps:
101) chemical formula Li is pressed7La3Zr2O12In elemental mole ratios weigh Li source compound, lanthanum source compound and zirconium source respectively
Object is closed, Li source compound and lanthanum source compound are dissolved in organic solvent, solution A is obtained；Zirconium source compound is dissolved in organic molten
In agent, and it is added dropwise to chelating agent in whipping process, obtains solution B；
102) solution A is mixed with solution B, obtains Li7La3Zr2O12Wet gel；
103) wet gel obtains Li through drying7La3Zr2O12Xerogel；
104) xerogel is put into cooling after being pre-sintered in agglomerating plant and obtains Li7La3Zr2O12Precursor powder；
105) precursor powder being prepared is subjected to Fast Sintering under inert gas protection, is cooled to room temperature to obtain
Li7La3Zr2O12Powder.
2. preparation method according to claim 1, which is characterized in that Fast Sintering in step 105 be microwave sintering, etc.
Ion activation sintering or field help sintering.
3. preparation method according to claim 1, which is characterized in that the Li source compound is lithium carbonate, lithium nitrate
One of with lithium acetate, lanthanum source compound is one of lanthana, lanthanum acetate and lanthanum nitrate, and zirconium source compound is dichloro oxygen
Change one of zirconium, zirconyl nitrate, ethyl alcohol zirconium and propyl alcohol zirconium；Organic solvent is methanol, ethyl alcohol, propyl alcohol, ethylene glycol, butanol, ring
At least one of oxidative ethane and dimethylbenzene, chelating agent are at least one in hydrochloric acid, acetic acid, boric acid, sulfuric acid, phosphoric acid and ammonium hydroxide
Kind.
4. preparation method according to claim 1, which is characterized in that in solution A, Li source compound and lanthanum source compound
The ratio between the sum of amount of substance and the volume of organic solvent be 1mmol:2ml~1mmol:20ml.
5. preparation method according to claim 1, which is characterized in that in solution B the amount of substance of zirconium source compound with it is organic
The ratio between volume of solvent is 1mmol:1ml~1mmol:8ml, and the mass ratio of zirconium source compound and chelating agent is 1:1~1:6.
6. preparation method according to claim 1, which is characterized in that in step 104), xerogel is placed in crucible,
It is put into cooling after being pre-sintered in agglomerating plant and obtains Li7La3Zr2O12Precursor powder；The crucible is oxidation zirconium crucible, oxygen
Change aluminium crucible or lanthana crucible.
7. preparation method according to claim 1, which is characterized in that the agglomerating plant in step 104) is Muffle furnace, pipe
Formula furnace, van-type furnace or vacuum drying oven.
8. preparation method according to claim 1, which is characterized in that the pre-sintering process in step 104) are as follows: heating speed
Rate is 2 DEG C/min~20 DEG C/min, and sintering temperature is 300 DEG C~500 DEG C, soaking time is 2h~3h.
9. preparation method according to claim 1, which is characterized in that the inert gas in step 105) is argon gas, helium
At least one of with nitrogen.
10. preparation method according to claim 1, which is characterized in that the Fast Sintering technique in step 105) are as follows: heating
Rate is 50~200 DEG C/min, and sintering temperature is 900 DEG C~1100 DEG C, soaking time is 1~30min.
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| CN115340378A (en) * | 2022-10-20 | 2022-11-15 | 江苏蓝固新能源科技有限公司 | Oxide solid electrolyte, preparation method thereof and lithium ion battery |
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| CN116779871A (en) * | 2023-08-24 | 2023-09-19 | 浙江帕瓦新能源股份有限公司 | Lithium lanthanum zirconate coated and modified cathode material, preparation method thereof and lithium ion battery |
| CN116779871B (en) * | 2023-08-24 | 2023-11-21 | 浙江帕瓦新能源股份有限公司 | Lithium lanthanum zirconate coated and modified cathode material, preparation method thereof and lithium ion battery |
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