CN109687019A - A method of improving oxide solid electrolyte electric conductivity - Google Patents
A method of improving oxide solid electrolyte electric conductivity Download PDFInfo
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- CN109687019A CN109687019A CN201910061101.2A CN201910061101A CN109687019A CN 109687019 A CN109687019 A CN 109687019A CN 201910061101 A CN201910061101 A CN 201910061101A CN 109687019 A CN109687019 A CN 109687019A
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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
- H01M10/052—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
- 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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Abstract
The invention discloses a kind of methods for improving oxide solid electrolyte electric conductivity.The specific method is as follows: clean oxide solid electrolyte being placed in tube furnace, to form gas offer lower than the oxygen atmosphere (anaerobic environment) in standard atmospheric pressure by being introduced into.Solid electrolyte is subjected to long-time the high temperature anneal under reducing atmosphere, obtained sample rapid quenching to room temperature.It can be artificially introduced the Lacking oxygen defect with ionic conductivity by such method, and then improve the ionic conducting property of oxide solid electrolyte.The invention is different from the method for changing oxidation physical performance by doping element, and operation is succinct, and effect is obvious, convenient for regulation, has excellent market application prospect.
Description
Technical field
The present invention relates to the modified field of solid electrolyte, in particular to a kind of improvement oxide solid electrolyte electric conductivities
Method.
Background technique
Rechargeable type new energy battery of the lithium ion battery as a new generation, it is inseparable with our daily life,
Electric vehicle (medium-sized passenger traffic is arrived from portable electronic product (mobile phone, tablet computer, laptop, digital camera etc.)
Vehicle, small-sized private car, small cargo vehicle), lithium ion battery all plays vital role.Compared to conventional lead acid electricity
Pond, lithium battery have high-energy density, and energy conversion efficiency is high, has extended cycle life, small in size, light weight is environmental-friendly etc. excellent
Point.Simultaneously, lithium ion battery also has problem to be solved itself, for example production cost is slightly higher, and preparation process is complicated, electricity
The operating temperature range in pond is limited.With the upgrading of industrial technology, production equipment working efficiency can be improved, in addition is produced from upstream
The large-scale production of industry chain is increasingly mature, can further decrease battery production cost.And cell safety problem, it is not only consumer
The most important thing in most concerned problem and new energy battery enterprise producing scientific research.Mainstream lithium-ion electric currently on the market
Pond uses organic liquid electrolytes, and battery is in abnormal use, excessive charge and discharge, and by fierce external mechanical impact
When, it is often accompanied by the generation of heat and the raising of internal temperature of battery.And _ _ thermal runaway can directly result in the inflatable of electrolyte, into
And lead to the spontaneous combustion and explosion of battery.
All-solid-state battery uses the solid electrolyte without inflammable volatile component, can be led with effective solution due to high temperature
The cell safety problem of cause and the operating temperature range for having widened battery, therefore more and more research concerns are also received,
With the potential quality for becoming next-generation mainstream business new energy battery.All-solid-state battery uses solid electrolyte from structure design
Organic electrolyte and diaphragm are substituted, battery structure is not only simplified, reduces battery volume, improves volume energy density,
Shorten manufacturing process, improves production efficiency.At the same time, with the improvement of battery safety, corresponding battery is cooling,
Heat management, outsourcing package module are also greatly simplified.From the angle for improving energy density, solid electrolyte can be with
Stablize, the core material with Li metal negative electrode material adapted composition high-energy density of safety.Although solid electrolyte has upper
Brilliant performance is stated, but compared with traditional organic liquid electrolytes, electric conductivity is slightly lower, directly affects lithium ion and exists
Transport efficiency in charge and discharge process.Therefore, the ionic conductivity for how improving solid electrolyte becomes the heat studied instantly
Point.Traditional modification mode is and then to improve its electric conductivity by mixing different elements into solid electrolyte.The method exists
It is more demanding in industrial production, strict control element incorporation is needed, operating procedure is cumbersome, and the element newly introduced may change solid
The original structure of state electrolyte and chemical property.
Therefore, the prior art requires further improvement.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of side for improving oxide solid electrolyte electric conductivity
Method.The present invention is directed to introduce the new modified technique of one kind to improve it under the premise of not destroying solid electrolyte script stability
Ionic conducting property.
To achieve the above object, the specific technical solution of the present invention is as follows:
A method of improving oxide solid electrolyte electric conductivity, which comprises the steps of:
(1) successively in acetone and a methanol by oxide solid electrolyte, high frequency ultrasound cleaning；
(2) solid electrolyte after cleaning is placed in tube furnace, gas component and air inlet is formed by regulation
Air-flow size forms the partial pressure of oxygen of reduction (low) in tube furnace, this partial pressure of oxygen is significantly lower than partial pressure of oxygen in standard atmospheric pressure；
(3) tubular type furnace temperature is increased, and under low oxygen partial pressure atmosphere, long term annealing is carried out to sample；
(4) sample rapid quenching to room temperature is then obtained into the oxide solid electrolyte of high conductivity.
As a preferred embodiment of the invention, oxide solid electrolyte is selected from Ca-Ti ore type Li3.3La0.56TiO3, sodium fastly from
Sub- conductor type LiTi2(PO4)3, lithium fast-ionic conductor type Li14Zn(GeO4)4, carbuncle type Li7La3Zr2O12One of.
As a preferred embodiment of the invention, oxide solid electrolyte is sequentially placed in acetone and methanol, in 40~80K
Under Hz high frequency, it is cleaned by ultrasonic 2~15min.
As a preferred embodiment of the invention, formation atmosphere used in tube furnace is 1%H2+ 99%Ar and/or
Ar。
As a preferred embodiment of the invention, tube furnace air inlet gas flow is 0.2~50m3/h。
As a preferred embodiment of the invention, the annealing temperature of oxide solid electrolyte is 900~1500 DEG C, annealing time
Be 8~for 24 hours.
As an of the invention preferred embodiment, the oxide solid electrolyte after annealing with 50~100 DEG C/s rapid quenching extremely
Room temperature.
Using technical solution of the present invention, have the advantages that
The present invention is high in anaerobic environment (lower than partial pressure of oxygen in normal atmosphere (An)) by the way that oxide solid electrolyte to be placed in
Temperature annealing, increases the Lacking oxygen defect density with ionic conductivity, and then improve the ion of oxide solid electrolyte
Electric conductivity.Compared to the method for modifying of doping element, the structure and chemical property of ring script solid electrolyte will not be broken.This
Outside, present invention process is simple, easy to operate, and repeatability is strong, is suitable for large-scale production, conducive to the industrialization of all-solid-state battery
Process.
Detailed description of the invention
Fig. 1 is the flow chart of the method for the present invention.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further described.
Shown in referring to Fig.1, the present invention provides a kind of method for improving oxide solid electrolyte electric conductivity, including as follows
Step:
S1, by oxide solid electrolyte successively in acetone and a methanol, high frequency ultrasound cleaning；
S2, the solid electrolyte after cleaning is placed in tube furnace, gas component and air inlet is formed by regulation
Air-flow size forms the partial pressure of oxygen of reduction in tube furnace, this partial pressure of oxygen is significantly lower than partial pressure of oxygen in standard atmospheric pressure；
S3, tubular type furnace temperature is increased, and under low oxygen partial pressure atmosphere, long term annealing is carried out to sample；
S4, then by sample rapid quenching to room temperature, obtain the oxide solid electrolyte of high conductivity.
According to the above method, several embodiments are given below, ionic conductivity can be obtained to prove method of the invention
Energy.
Embodiment 1
By Li3.3La0.56TiO3Solid electrolyte is put into acetone ultrasonic (40K Hz) cleaning 10min, is then placed in methanol
Medium-high frequency ultrasound (40K Hz) cleans 10min.Use N2Drying sample, and sample is placed in tube furnace.Into tube furnace
It is passed through Ar, and controlling Ar throughput is 10m3/h.Under this specific partial pressure of oxygen, heating sample to 900 DEG C annealing for 24 hours, then
It is rapidly cooled to room temperature with the speed of 50 DEG C/s.
After tested, the Li after annealing3.3La0.56TiO3No change has taken place for the crystal structure of solid electrolyte, room
Warm electric conductivity is from 10-3S/cm rises to 2 × 10-3S/cm。
Embodiment 2
By Li3.3La0.56TiO3Solid electrolyte is put into acetone ultrasonic (60K Hz) cleaning 8min, is then placed in methanol
High frequency ultrasound (60K Hz) cleans 8min.Use N2Drying sample, and sample is placed in tube furnace.It is passed through into tube furnace
Ar, and controlling Ar throughput is 80m3/h.Under this specific partial pressure of oxygen, sample is heated to 1100 DEG C of annealing 16h, then with 70
DEG C/speed of s is rapidly cooled to room temperature.
After tested, the Li after annealing3.3La0.56TiO3No change has taken place for the crystal structure of solid electrolyte, room
Warm electric conductivity is from 10-3S/cm rises to 3x10-3S/cm。
Embodiment 3
By Li3.3La0.56TiO3Solid electrolyte is put into acetone ultrasonic (80K Hz) cleaning 6min, is then placed in methanol
High frequency ultrasound (80K Hz) cleans 6min.Use N2Drying sample, and sample is placed in tube furnace.It is passed through into tube furnace
Ar and formation gas (1%H2+ 99%Ar), and controlling Ar throughput is 50m3/ h, forming gas flow is 20m3/h.Herein
Under specific partial pressure of oxygen, sample is heated to 1300 DEG C of annealing 10h, is then rapidly cooled to room temperature with the speed of 80 DEG C/s.
After tested, the Li after annealing3.3La0.56TiO3No change has taken place for the crystal structure of solid electrolyte, room
Warm electric conductivity is from 10-3S/cm rises to 6 × 10-3S/cm。
Embodiment 4
By Li3.3La0.56TiO3Solid electrolyte is put into acetone ultrasonic (100K Hz) cleaning 5min, is then placed in methanol
Medium-high frequency ultrasound (100K Hz) cleans 5min.Use N2Drying sample, and sample is placed in tube furnace.Into tube furnace
It is passed through to form gas (1%H2+ 99%Ar), and control and form gas flow as 50m3/h.Under this specific partial pressure of oxygen, heating
Sample is then rapidly cooled to room temperature to 1500 DEG C of annealing 8h with the speed of 100 DEG C/s.
After tested, the Li after annealing3.3La0.56TiO3No change has taken place for the crystal structure of solid electrolyte, room
Warm electric conductivity is from 10-3S/cm rises to 8x 10-3S/cm。
Embodiment 5
By LiTi2(PO4)3Solid electrolyte is put into acetone ultrasonic (40K Hz) cleaning 10min, is then placed in methanol
High frequency ultrasound (40K Hz) cleans 10min.Use N2Drying sample, and sample is placed in tube furnace.Lead into tube furnace
Enter Ar, and controlling Ar throughput is 10m3/h.Under this specific partial pressure of oxygen, heating sample to 900 DEG C annealing for 24 hours, then with
The speed of 50 DEG C/s is rapidly cooled to room temperature.
After tested, the LiTi after annealing2(PO4)3No change has taken place for the crystal structure of solid electrolyte, room temperature
Electric conductivity is from very low (< 10-5S/cm 1x10) is risen to-4S/cm。
Embodiment 6
By LiTi2(PO4)3Solid electrolyte is put into acetone ultrasonic (60K Hz) cleaning 8min, is then placed in methanol high
Frequency ultrasonic (60K Hz) cleans 8min.Use N2Drying sample, and sample is placed in tube furnace.It is passed through into tube furnace
Ar, and controlling Ar throughput is 80m3/h.Under this specific partial pressure of oxygen, sample is heated to 1100 DEG C of annealing 16h, then with 70
DEG C/speed of s is rapidly cooled to room temperature.
After tested, the LiTi after annealing2(PO4)3No change has taken place for the crystal structure of solid electrolyte, room temperature
Electric conductivity is from very low (< 10-5S/cm 4 × 10) are risen to-4S/cm。
Embodiment 7
By LiTi2(PO4)3Solid electrolyte is put into acetone ultrasonic (80K Hz) cleaning 6min, is then placed in methanol high
Frequency ultrasonic (80K Hz) cleans 6min.Use N2Drying sample, and sample is placed in tube furnace.Ar is passed through into tube furnace
With formation gas (1%H2+ 99%Ar), and controlling Ar throughput is 50m3/ h, forming gas flow is 20m3/h.It is special herein
Determine under partial pressure of oxygen, heats sample to 1300 DEG C of annealing 10h, be then rapidly cooled to room temperature with the speed of 80 DEG C/s.
After tested, the LiTi after annealing2(PO4)3No change has taken place for the crystal structure of solid electrolyte, room temperature
Electric conductivity is from very low (< 10-5S/cm 5 × 10) are risen to-4S/cm。
Embodiment 8
By LiTi2(PO4)3Solid electrolyte is put into acetone ultrasonic (100K Hz) cleaning 5min, is then placed in methanol
High frequency ultrasound (100K Hz) cleans 5min.Use N2Drying sample, and sample is placed in tube furnace.Lead into tube furnace
Enter to be formed gas (1%H2+ 99%Ar), and control and form gas flow as 50m3/h.Under this specific partial pressure of oxygen, sample is heated
Product are then rapidly cooled to room temperature to 1500 DEG C of annealing 8h with the speed of 100 DEG C/s.
After tested, the LiTi after annealing2(PO4)3No change has taken place for the crystal structure of solid electrolyte, room temperature
Electric conductivity is from very low (< 10-5S/cm 8 × 10) are risen to-4S/cm。
Embodiment 9
By Li14Zn(GeO4)4Solid electrolyte is put into acetone ultrasonic (40K Hz) cleaning 10min, is then placed in methanol
Medium-high frequency ultrasound (40K Hz) cleans 10min.Use N2Drying sample, and sample is placed in tube furnace.Into tube furnace
It is passed through Ar, and controlling Ar throughput is 10m3/h.Under this specific partial pressure of oxygen, heating sample to 900 DEG C annealing for 24 hours, then
It is rapidly cooled to room temperature with the speed of 50 DEG C/s.
After tested, the Li after annealing14Zn(GeO4)4No change has taken place for the crystal structure of solid electrolyte, room
Warm electric conductivity is from very low (< 10-5S/cm 9 × 10) are risen to-5S/cm。
Embodiment 10
By Li14Zn(GeO4)4Solid electrolyte is put into acetone ultrasonic (60K Hz) cleaning 8min, is then placed in methanol
High frequency ultrasound (60K Hz) cleans 8min.Use N2Drying sample, and sample is placed in tube furnace.It is passed through into tube furnace
Ar, and controlling Ar throughput is 80m3/h.Under this specific partial pressure of oxygen, sample is heated to 1100 DEG C of annealing 16h, then with 70
DEG C/speed of s is rapidly cooled to room temperature.
After tested, the Li after annealing14Zn(GeO4)4No change has taken place for the crystal structure of solid electrolyte, room
Warm electric conductivity is from very low (< 10-5S/cm 3 × 10) are risen to-4S/cm。
Embodiment 11
By Li14Zn(GeO4)4Solid electrolyte is put into acetone ultrasonic (80K Hz) cleaning 6min, is then placed in methanol
High frequency ultrasound (80K Hz) cleans 6min.Use N2Drying sample, and sample is placed in tube furnace.It is passed through into tube furnace
Ar and formation gas (1%H2+ 99%Ar), and controlling Ar throughput is 50m3/ h, forming gas flow is 20m3/h.Herein
Under specific partial pressure of oxygen, sample is heated to 1300 DEG C of annealing 10h, is then rapidly cooled to room temperature with the speed of 80 DEG C/s.
After tested, the Li after annealing14Zn(GeO4)4No change has taken place for the crystal structure of solid electrolyte, room
Warm electric conductivity is from very low (< 10-5S/cm 7 × 10) are risen to-4S/cm。
Embodiment 12
By Li14Zn(GeO4)4Solid electrolyte is put into acetone ultrasonic (100K Hz) cleaning 5min, is then placed in methanol
Medium-high frequency ultrasound (100K Hz) cleans 5min.Use N2Drying sample, and sample is placed in tube furnace.Into tube furnace
It is passed through to form gas (1%H2+ 99%Ar), and control and form gas flow as 50m3/h.Under this specific partial pressure of oxygen, heating
Sample is then rapidly cooled to room temperature to 1500 DEG C of annealing 8h with the speed of 100 DEG C/s.
After tested, the Li after annealing14Zn(GeO4)4No change has taken place for the crystal structure of solid electrolyte, room
Warm electric conductivity is from very low (< 10-5S/cm 8 × 10) are risen to-4S/cm。
Embodiment 13
By Li7La3Zr2O12Solid electrolyte is put into acetone ultrasonic (40K Hz) cleaning 10min, is then placed in methanol
High frequency ultrasound (40K Hz) cleans 10min.Use N2Drying sample, and sample is placed in tube furnace.Lead into tube furnace
Enter Ar, and controlling Ar throughput is 10m3/h.Under this specific partial pressure of oxygen, heating sample to 900 DEG C annealing for 24 hours, then with
The speed of 50 DEG C/s is rapidly cooled to room temperature.
After tested, the Li after annealing7La3Zr2O12No change has taken place for the crystal structure of solid electrolyte, room temperature
Electric conductivity is from about < 10-3S/cm rises to 3 × 10-3S/cm。
Embodiment 14
By Li7La3Zr2O12Solid electrolyte is put into acetone ultrasonic (60K Hz) cleaning 8min, is then placed in methanol high
Frequency ultrasonic (60K Hz) cleans 8min.Use N2Drying sample, and sample is placed in tube furnace.It is passed through into tube furnace
Ar, and controlling Ar throughput is 80m3/h.Under this specific partial pressure of oxygen, sample is heated to 1100 DEG C of annealing 16h, then with 70
DEG C/speed of s is rapidly cooled to room temperature.
After tested, the Li after annealing7La3Zr2O12No change has taken place for the crystal structure of solid electrolyte, room temperature
Electric conductivity is from about < 10-3S/cm rises to 4 × 10-3S/cm。
Embodiment 15
By Li7La3Zr2O12Solid electrolyte is put into acetone ultrasonic (80K Hz) cleaning 6min, is then placed in methanol high
Frequency ultrasonic (80K Hz) cleans 6min.Use N2Drying sample, and sample is placed in tube furnace.Ar is passed through into tube furnace
With formation gas (1%H2+ 99%Ar), and controlling Ar throughput is 50m3/ h, forming gas flow is 20m3/h.It is special herein
Determine under partial pressure of oxygen, heats sample to 1300 DEG C of annealing 10h, be then rapidly cooled to room temperature with the speed of 80 DEG C/s.
After tested, the Li after annealing7La3Zr2O12No change has taken place for the crystal structure of solid electrolyte, room temperature
Electric conductivity is from about < 10-3S/cm rises to 7 × 10-3S/cm。
Embodiment 16
By Li7La3Zr2O12Solid electrolyte is put into acetone ultrasonic (100K Hz) cleaning 5min, is then placed in methanol
High frequency ultrasound (100K Hz) cleans 5min.Use N2Drying sample, and sample is placed in tube furnace.Lead into tube furnace
Enter to be formed gas (1%H2+ 99%Ar), and control and form gas flow as 50m3/h.Under this specific partial pressure of oxygen, sample is heated
Product are then rapidly cooled to room temperature to 1500 DEG C of annealing 8h with the speed of 100 DEG C/s.
After tested, the Li after annealing7La3Zr2O12No change has taken place for the crystal structure of solid electrolyte, room temperature
Electric conductivity is from about < 10-3S/cm rises to 1 × 10-2S/cm。
It is obtained from above-described embodiment inspection result, the oxide solid electrolyte by low oxygen partial pressure annealing is in room
Conductivity when conductivity under temperature is all larger than unprocessed, it was demonstrated that such method can effectively solve oxide solid electrolyte
The not high problem of ionic conductance performance.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by description of the invention and accompanying drawing content, or directly/use indirectly
It is included in other related technical areas in scope of patent protection of the invention.
Claims (7)
1. a kind of method for improving oxide solid electrolyte electric conductivity, which comprises the steps of:
(1) successively in acetone and a methanol by oxide solid electrolyte, high frequency ultrasound cleaning；
(2) solid electrolyte after cleaning is placed in tube furnace, gas component and air inlet stream is formed by regulation
Size forms the partial pressure of oxygen of reduction in tube furnace, this partial pressure of oxygen is significantly lower than partial pressure of oxygen in standard atmospheric pressure；
(3) tubular type furnace temperature is increased, and under low oxygen partial pressure atmosphere, long term annealing is carried out to sample；
(4) sample rapid quenching to room temperature is then obtained into the oxide solid electrolyte of high conductivity.
2. the method according to claim 1 for improving oxide solid electrolyte electric conductivity, it is characterised in that: oxide
Solid electrolyte is selected from Ca-Ti ore type Li3.3La0.56TiO3, Fast ion conductor type LiTi2(PO4)3, lithium fast-ionic conductor type
Li14Zn(GeO4)4, carbuncle type Li7La3Zr2O12One of.
3. the method according to claim 1 for improving oxide solid electrolyte electric conductivity, it is characterised in that: oxide
Solid electrolyte is sequentially placed in acetone and methanol, under 40~80K Hz high frequency, is cleaned by ultrasonic 2~15min.
4. the method according to claim 1 for improving oxide solid electrolyte electric conductivity, it is characterised in that: tube furnace
Used in formation atmosphere be 1%H2+ 99%Ar and/or Ar.
5. the method according to claim 1 for improving oxide solid electrolyte electric conductivity, it is characterised in that: tube furnace
Air inlet gas flow is 0.2~50m3/h。
6. the method according to claim 1 for improving oxide solid electrolyte electric conductivity, it is characterised in that: oxide
The annealing temperature of solid electrolyte is 900~1500 DEG C, annealing time is 8~for 24 hours.
7. the method according to claim 1 for improving oxide solid electrolyte electric conductivity, it is characterised in that: after annealing
Oxide solid electrolyte with 50~100 DEG C/s rapid quenching to room temperature.
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| CN112563575A (en) * | 2020-12-08 | 2021-03-26 | 上海电力大学 | Composite solid electrolyte with transition molybdenum trioxide as filler, preparation method and application |
| CN113690482A (en) * | 2021-08-03 | 2021-11-23 | 深圳先进技术研究院 | Solid electrolyte crystal interface processing method, solid electrolyte and solid battery |
| CN114373881A (en) * | 2021-12-17 | 2022-04-19 | 东北大学 | Surface modification method of lithium-rich manganese-based positive electrode material based on reducing atmosphere treatment |
| CN117976969A (en) * | 2024-03-28 | 2024-05-03 | 深圳欣界能源科技有限公司 | Method for producing solid electrolyte containing oxygen vacancy and solid battery |
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| CN107681195A (en) * | 2017-09-06 | 2018-02-09 | 重庆大学 | The preparation method of nanometer garnet-type solid electrolyte material |
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| CN114373881A (en) * | 2021-12-17 | 2022-04-19 | 东北大学 | Surface modification method of lithium-rich manganese-based positive electrode material based on reducing atmosphere treatment |
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