CN109301315A - Solid electrolyte powder and preparation method thereof - Google Patents
Solid electrolyte powder and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种固态电解质粉末及其制备方法，将碳酸锂、氧化镧、氧化钽和氧化锆按照一定的比例混合，转移至马弗炉中固相烧结，冷却至室温后进行球磨，降低颗粒度后，在惰性气氛中进行热处理，从而获得一种颗粒度在微纳米级别的含锂石榴石电解质粉末。与现有的技术相比，本发明所制备得到的电解质具有高的锂离子传导率、高纯度(有效降低表层碳酸锂)、对金属锂稳定等优点。
The invention relates to a solid electrolyte powder and a preparation method thereof. Lithium carbonate, lanthanum oxide, tantalum oxide and zirconia are mixed in a certain proportion, transferred to a muffle furnace for solid-phase sintering, cooled to room temperature, and then ball-milled to reduce particle size. After the temperature, heat treatment is performed in an inert atmosphere, thereby obtaining a lithium-containing garnet electrolyte powder with a particle size in the micro-nano scale. Compared with the prior art, the electrolyte prepared by the present invention has the advantages of high lithium ion conductivity, high purity (effectively reducing lithium carbonate in the surface layer), and stability to metallic lithium.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of solid electrolyte powder and preparation method thereof.
Background technique
Lithium ion battery has been widely applied in the production and living of people as one of most important energy storage device,
Energy density, capacity density and the safety for how further increasing battery, always are the emphasis of Study on Li-ion batteries,
It is the hot spot of energy industry in recent years.With the development of world economy and science and technology, electronics and automobile industry want energy storage device
Ask higher and higher, important composition of the lithium battery as energy storage device has great development space.Wherein electrolyte is as lithium electricity
The mostly important component part in pond plays a part of transmitting lithium ion in lithium ion battery, for maintain battery system
Stable circulation, the high rate performance for promoting battery have great significance.Lithium ion battery applied currently on the market nearly all exists
Using liquid electrolyte, but there is many drawbacks among these, such as LiPF common in lithium salts6It is easy to be decomposed to form HF,
Organic solvent itself has the characteristics that inflammable and explosive, and all there is safety problems for these.In particular with market for battery energy
The pursuit of metric density and capacity density, security issues become increasingly urgent for liquid electrolyte.
In traditional lithium ion battery, positive and negative pole material is solid-state conductive material, electrolyte be liquid or colloid from
Sub- conductor.When battery is hit or is under hot environment, it is easy to happen explosion.Also, with market for
The energy density of lithium ion battery is constantly asked, and the electrode potential of positive electrode is higher and higher, and oxidisability is strong, while in order to pursue body
Product density also diaphragm is constantly thinned, the continuous development in the two extreme directions, and the short circuit explosion for resulting in inside battery may
Property be continuously improved.In order to fundamentally solve the safety issue of battery, almost all of battery power researcher is proposed
The research direction of solid electrolyte powder.
Solid electrolyte is roughly divided into organic solid-state electrolyte and inorganic solid electrolyte.Inorganic solid electrolyte is by height
Coordination metal ion composition polyhedron skeleton and can free shuttling in stablize in skeleton mobile lithium ion composition crystal
Or it is noncrystal.The electrical conduction mechanism of inorganic electrolyte is, compared with ideal crystal lattice, there is each for actual crystal kind
The unordered atom of kind, including gap and interstitial atom, in some compounds, since drawbacks described above structure is relatively more, greatly
The ion of amount is in unordered state, becomes so-called disordered structure, and ion can jump to another position from a position
It sets, so that ionic conduction is produced, what is particularly worth mentioning is that, when the activation energy required for jumping is lower, ion-conductance
Conductance can be suitable with liquid electrolyte.Inorganic solid-state lithium ion conductor has many compared to the liquid electrolyte used now
Advantage for example, higher thermal stability, does not reveal and pollute, and has very big electrochemical stability window.In addition, containing
High elasticity modulus makes that it is suitable for stiffness films batteries in lithium garnet.Current inorganic solid-state lithium ion conductor can be divided into
Four kinds: NASICON type, Ca-Ti ore type, LIPON type and carbuncle type below.
In various solid electrolytes, garnet containing lithium (hereinafter referred to as LLZO) causes the pole of scientific researcher
Big interest, it and electrode have good chemical stability and electrochemical stability, and room temperature conductivity is higher by (> 10-4S/cm).In
2003, solid-phase sintering method is used to synthesize garnet containing lithium for the first time by team such as Thangadurai, then, this performance
Excellent electrolyte garnet material containing lithium receives the concern of more and more researchers.LLZO is a kind of the quick of lithium ion
Conductor has this high room temperature conductivity, high mechanical strength, while high stability and chemical stabilization being presented to lithium metal
Property.
Although LLZO haves many advantages, such as, production and application apart from the marketization still have biggish distance.Lei
The case where Cheng team is calculated by DFT, simulates LLZO exposure in air, wherein there are two kinds of generation surface lithium carbonates
Process, and the lithium carbonate of this 10~100nm thickness significantly impacts the interface performance to lithium metal, so that interface resistance increases
Nearly an order of magnitude.Simultaneously as LLZO hardness itself is higher, it is difficult to be matched very well with positive and negative anodes, in order to solve this
A problem, more and more scientific researchers use garnet containing lithium-polymer composite and flexible electrolyte, thus in order to be promoted and
The matching of positive and negative anodes reduces interface resistance, and the stone powder of pomegranate containing lithium for how obtaining high-purity just becomes flexible compound electrolysis
The crucial first step of matter.Therefore the method that one kind is efficient, at low cost, repetitive rate is high is developed to prepare with high-purity cubic phase
The solid-state electrolyte powder of garnet containing lithium have a very important significance.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of efficient, at low cost
Solid electrolyte powder and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions: a kind of solid electrolyte powder, the solid state electrolysis
The crystal phase of matter powder is cubic phase garnet structure, and includes lithia, lanthana, zirconium oxide in the solid electrolyte powder
And tantalum oxide, the lithia, lanthana, zirconium oxide and tantalum oxide mass ratio be (6~10.1): (45~50): (15~
20): (10~15).Under normal circumstances, the surface of garnet containing lithium is easy to generate lithium carbonate in air atmosphere, can significantly improve
To the interface resistance of lithium metal, and the present invention is exactly based on heat treatment to reduce the lithium carbonate on pomegranate stone powder surface to improve
To the interface performance of lithium metal.
A kind of preparation method of solid electrolyte powder as described above, comprising the following steps:
(1) lithium carbonate, lanthana, zirconium oxide and tantalum oxide are mixed, and are ground by dry milling processes, is then sintered,
Obtain solid-phase reactant；
(2) solid-phase reactant is subjected to ball milling, is transferred to after dry and is heat-treated under an inert atmosphere, is subsequently cooled to
Room temperature is to get the solid electrolyte powder.
The lithium carbonate, lanthana, zirconium oxide and tantalum oxide mass ratio be (15~25): (45~50): (15~
20): (10~15).In actual fabrication process, lithium carbonate can suitably excessively be volatilized with compensating the lithium being sintered under high temperature.
The time of the dry grinding is 45~90min.
The sintering uses following condition: be warming up to 850~900 DEG C with the temperature rise of 2~10 DEG C/min, then keep the temperature 2~
Then 6h is warming up to 1100~1200 DEG C with the temperature rise of 2~10 DEG C/min, then keep the temperature 10~25h.In this sintering process,
Former mixing forms tetragonal phase crystal form at 900 DEG C first, after a period of stabilisation, a cube phase structure is formd at 1150 DEG C, right
For garnet structure containing lithium, the latter has higher lithium ion conductivity (10-3~10-4S/cm or so).
The ball milling using one of isopropanol, methyl methacrylate or hexamethylene as ball milling agent, the ball milling
Revolving speed is 500~1000r/min, and Ball-milling Time is 10~60min.Grinding agent is using isopropanol or methyl methacrylate
Ester or hexamethylene.The purpose of this process is to reduce the granularity of the stone powder of pomegranate containing lithium.
The heat treatment uses following condition: being warming up to 500~800 DEG C with the temperature rise of 2~10 DEG C/min, then keeps the temperature 2
~10h.
The inert atmosphere is slumpability gas.In order to reduce high temperature sintering temperature-fall period and mechanical milling process pomegranate containing lithium
The lithium carbonate that stone surface is formed, subsequent step are heat-treated in an inert atmosphere by the way of heat treatment, pass through reduction
The decomposable process of carbon dioxide divided to promote lithium carbonate.It is hereby achieved that the electrolyte powder of garnet containing lithium of high-purity
End.
Compared with prior art, the beneficial effects of the present invention are embodied in following several respects:
(1) the carbonic acid lithium content on solid electrolyte surface of the invention is extremely low, has high lithium ion conductivity, high-purity
The advantages that spending, stablizing to lithium metal, can be effectively reduced interface resistance；
(2) preparation method of the invention is efficient, at low cost and repetitive rate is high.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the stone powder of pomegranate containing lithium of preparation；
Fig. 2 is the Raman comparison diagram of the stone powder of pomegranate containing the lithium heat treatment front and back of preparation；
Fig. 3 is the XPS comparison diagram of the stone powder of pomegranate containing the lithium heat treatment front and back of preparation；
Fig. 4 is the electron microscope of the stone powder of pomegranate containing lithium of preparation.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
Step 1: being 15%, 50%, 20% and 15% successively to weigh lithium carbonate, lanthana, oxygen respectively according to mass fraction
Change zirconium and tantalum oxide, siccative is ground 15 minutes, when replacing wet-milling that can shorten the volatilization of wet-milling solvent to a certain extent using dry grinding
Between, improve production efficiency.
Step 2: above-mentioned mixture is placed in crucible with cover, it is sintered in Muffle furnace.The temperature of sintering is
950 DEG C are risen to 5 DEG C/min heating rate, and keeps the temperature 2 hours at 950 DEG C, so that said mixture initial reaction, forms
The garnet containing lithium of tetragonal phase.Then continue to be warming up to 1200 DEG C with the rate of 5 DEG C/min, and heat preservation 10 is small at such a temperature
When, be conducive to the formation of cubic phase and the stabilization procedures of cubic phase at this time.Subsequent furnace cooling takes out to room temperature and obtains mother
Powder.
Step 3: the female powder in step 2 is transferred in high energy ball mill, appropriate ball milling agent isopropanol is added to covering
Whole female powders, are arranged revolving speed 800r/min, and effective milling time is 40min.It is dried after ball milling.
Step 4: the product of step 3 kind is transferred in tube furnace, in an inert atmosphere, with the heating speed of 5 DEG C/min
Rate rises to 650 DEG C, and keeps the temperature 6 hours at 650 DEG C.This process purpose be by reduce carbon dioxide partial pressure,
To promote the decomposition of a small amount of lithium carbonate in female powder surface, the cubic phase stone powder of pomegranate containing lithium of higher purity is obtained.It is cooled to room
Wen Hou takes out product from tube furnace, obtains the electrolyte powder of garnet containing lithium of high-purity.
The garnet electrolyte powder that the step of the present embodiment is prepared carries out XRD characterization, obtained diffraction pattern
Spectrum is as shown in Figure 1, cubic phase garnet PDF card containing lithium (JCPDS NO.45-0109) with standard compares, it can be seen that
The garnet containing lithium that the method is prepared is pure cube phase structure, without other impurities.
Embodiment 2
Step 1: being 20%, 50%, 20% and 10% successively to weigh lithium carbonate, lanthana, oxygen respectively according to mass fraction
Change zirconium and tantalum oxide, siccative is ground 50 minutes, when replacing wet-milling that can shorten the volatilization of wet-milling solvent to a certain extent using dry grinding
Between, improve production efficiency.
Step 2: above-mentioned mixture is placed in crucible with cover, it is sintered in Muffle furnace.The temperature of sintering is
900 DEG C are risen to 5 DEG C/min heating rate, and keeps the temperature 4 hours at 900 DEG C, so that said mixture initial reaction, forms
The garnet containing lithium of tetragonal phase.Then continue to be warming up to 1150 DEG C with the rate of 5 DEG C/min, and heat preservation 16 is small at such a temperature
When, be conducive to the formation of cubic phase and the stabilization procedures of cubic phase at this time.Subsequent furnace cooling takes out to room temperature and obtains mother
Powder.
Step 3: the female powder in step 2 is transferred in high energy ball mill, appropriate ball milling agent isopropanol is added to covering
Whole female powders, are arranged revolving speed 800r/min, and effective milling time is 40min.It is dried after ball milling.
Step 4: the product of step 3 kind is transferred in tube furnace, in an inert atmosphere, with the heating speed of 5 DEG C/min
Rate rises to 650 DEG C, and keeps the temperature 6 hours at 650 DEG C.This process purpose be by reduce carbon dioxide partial pressure,
To promote the decomposition of a small amount of lithium carbonate in female powder surface, the cubic phase stone powder of pomegranate containing lithium of higher purity is obtained.It is cooled to room
Wen Hou takes out product from tube furnace, obtains the electrolyte powder of garnet containing lithium of high-purity.
The sample in the present embodiment before and after heat treatment step is tested using the method for Raman characterization, as shown in Fig. 2, in Re Chu
It is 200cm respectively before reason-1And 700cm-1Nearby detect the correspondence peak of lithium carbonate, and after Overheating Treatment, sample does not have
Detect the correspondence peak of any lithium carbonate, it can be seen that, heat treatment can effectively reduce the lithium carbonate on the surface of garnet containing lithium.
Embodiment 3
Step 1: being 25%, 50%, 15% and 10% successively to weigh lithium carbonate, lanthana, oxygen respectively according to mass fraction
Change zirconium and tantalum oxide, siccative is ground 60 minutes, when replacing wet-milling that can shorten the volatilization of wet-milling solvent to a certain extent using dry grinding
Between, improve production efficiency.
Step 2: above-mentioned mixture is placed in crucible with cover, it is sintered in Muffle furnace.The temperature of sintering is
850 DEG C are risen to 5 DEG C/min heating rate, and keeps the temperature 6 hours at 850 DEG C, so that said mixture initial reaction, forms
The garnet containing lithium of tetragonal phase.Then continue to be warming up to 1100 DEG C with the rate of 5 DEG C/min, and heat preservation 25 is small at such a temperature
When, be conducive to the formation of cubic phase and the stabilization procedures of cubic phase at this time.Subsequent furnace cooling takes out to room temperature and obtains mother
Powder.
Step 3: the female powder in step 2 is transferred in high energy ball mill, appropriate ball milling agent isopropanol is added to covering
Whole female powders, are arranged revolving speed 800r/min, and effective milling time is 40min.It is dried after ball milling.
Step 4: the product of step 3 kind is transferred in tube furnace, in an inert atmosphere, with the heating speed of 2 DEG C/min
Rate rises to 600 DEG C, and keeps the temperature 2 hours at 600 DEG C.This process purpose be by reduce carbon dioxide partial pressure,
To promote the decomposition of a small amount of lithium carbonate in female powder surface, the cubic phase stone powder of pomegranate containing lithium of higher purity is obtained.It is cooled to room
Wen Hou takes out product from tube furnace, obtains the electrolyte powder of garnet containing lithium of high-purity.
The sample in the present embodiment before and after heat treatment step, such as Fig. 3 are tested using the method for X-ray photoelectron spectroscopic analysis
Shown, after Overheating Treatment, the corresponding peak value of lithium carbonate can be substantially reduced, it means that heat-treating methods can be effective
Reduce the carbonic acid lithium content on the surface of garnet containing lithium.
Embodiment 4
Step 1: being 20%, 50%, 15% and 15% successively to weigh lithium carbonate, lanthana, oxygen respectively according to mass fraction
Change zirconium and tantalum oxide, siccative is ground 65 minutes, when replacing wet-milling that can shorten the volatilization of wet-milling solvent to a certain extent using dry grinding
Between, improve production efficiency.
Step 2: above-mentioned mixture is placed in crucible with cover, it is sintered in Muffle furnace.The temperature of sintering is
900 DEG C are risen to 5 DEG C/min heating rate, and keeps the temperature 4 hours at 900 DEG C, so that said mixture initial reaction, forms
The garnet containing lithium of tetragonal phase.Then continue to be warming up to 1150 DEG C with the rate of 5 DEG C/min, and heat preservation 16 is small at such a temperature
When, be conducive to the formation of cubic phase and the stabilization procedures of cubic phase at this time.Subsequent furnace cooling takes out to room temperature and obtains mother
Powder.
Step 3: the female powder in step 2 is transferred in high energy ball mill, appropriate ball milling agent methyl methacrylate is added
Revolving speed 800r/min is arranged to whole female powders are covered in ester, and effective milling time is 40min.It is dried after ball milling.
Step 4: the product of step 3 kind is transferred in tube furnace, in an inert atmosphere, with the heating speed of 2 DEG C/min
Rate rises to 800 DEG C, and keeps the temperature 2 hours at 800 DEG C.This process purpose be by reduce carbon dioxide partial pressure,
To promote the decomposition of a small amount of lithium carbonate in female powder surface, the cubic phase stone powder of pomegranate containing lithium of higher purity is obtained.It is cooled to room
Wen Hou takes out product from tube furnace, obtains the electrolyte powder of garnet containing lithium of high-purity.
The stone powder of pomegranate containing lithium finally obtained in the present embodiment is characterized using the method that electronic scanner microscope is analyzed, is led to
Crossing Fig. 4 can be seen that the powder particle size of garnet containing lithium that the embodiment obtains is different, and most of order of magnitude at 10 microns is left
It is right.
Embodiment 5
Step 1: being 20%, 45%, 20% and 15% successively to weigh lithium carbonate, lanthana, oxygen respectively according to mass fraction
Change zirconium and tantalum oxide, siccative is ground 70 minutes, when replacing wet-milling that can shorten the volatilization of wet-milling solvent to a certain extent using dry grinding
Between, improve production efficiency.
Step 2: above-mentioned mixture is placed in crucible with cover, it is sintered in Muffle furnace.The temperature of sintering is
900 DEG C are risen to 5 DEG C/min heating rate, and keeps the temperature 4 hours at 900 DEG C, so that said mixture initial reaction, forms
The garnet containing lithium of tetragonal phase.Then continue to be warming up to 1150 DEG C with the rate of 5 DEG C/min, and heat preservation 16 is small at such a temperature
When, be conducive to the formation of cubic phase and the stabilization procedures of cubic phase at this time.Subsequent furnace cooling takes out to room temperature and obtains mother
Powder.
Step 3: the female powder in step 2 is transferred in high energy ball mill, appropriate ball milling agent methyl methacrylate is added
Revolving speed 800r/min is arranged to whole female powders are covered in ester, and effective milling time is 40min.It is dried after ball milling.
Step 4: the product of step 3 kind is transferred in tube furnace, in an inert atmosphere, with the heating speed of 10 DEG C/min
Rate rises to 500 DEG C, and keeps the temperature 10 hours at 500 DEG C.This process purpose be by reduce carbon dioxide partial pressure,
To promote the decomposition of a small amount of lithium carbonate in female powder surface, the cubic phase stone powder of pomegranate containing lithium of higher purity is obtained.It is cooled to room
Wen Hou takes out product from tube furnace, obtains the electrolyte powder of garnet containing lithium of high-purity.
Embodiment 6
Step 1: being 20%, 45%, 20% and 15% successively to weigh lithium carbonate, lanthana, oxygen respectively according to mass fraction
Change zirconium and tantalum oxide, siccative is ground 75 minutes, when replacing wet-milling that can shorten the volatilization of wet-milling solvent to a certain extent using dry grinding
Between, improve production efficiency.
Step 2: above-mentioned mixture is placed in crucible with cover, it is sintered in Muffle furnace.The temperature of sintering is
900 DEG C are risen to 10 DEG C/min heating rate, and keeps the temperature 4 hours at 900 DEG C, so that said mixture initial reaction, shape
At the garnet containing lithium of tetragonal phase.Then continue to be warming up to 1150 DEG C with the rate of 10 DEG C/min, and keeps the temperature 16 at such a temperature
Hour, be conducive to the formation of cubic phase and the stabilization procedures of cubic phase at this time.Then furnace cooling is obtained to room temperature, taking-up
Female powder.
Step 3: the female powder in step 2 is transferred in high energy ball mill, appropriate ball milling agent methyl methacrylate is added
Revolving speed 500r/min is arranged to whole female powders are covered in ester, and effective milling time is 60min.It is dried after ball milling.
Step 4: the product of step 3 kind is transferred in tube furnace, in an inert atmosphere, with the heating speed of 10 DEG C/min
Rate rises to 500 DEG C, and keeps the temperature 10 hours at 500 DEG C.This process purpose be by reduce carbon dioxide partial pressure,
To promote the decomposition of a small amount of lithium carbonate in female powder surface, the cubic phase stone powder of pomegranate containing lithium of higher purity is obtained.It is cooled to room
Wen Hou takes out product from tube furnace, obtains the electrolyte powder of garnet containing lithium of high-purity.
Embodiment 7
Step 1: being 20%, 45%, 20% and 15% successively to weigh lithium carbonate, lanthana, oxygen respectively according to mass fraction
Change zirconium and tantalum oxide, siccative is ground 80 minutes, when replacing wet-milling that can shorten the volatilization of wet-milling solvent to a certain extent using dry grinding
Between, improve production efficiency.
Step 2: above-mentioned mixture is placed in crucible with cover, it is sintered in Muffle furnace.The temperature of sintering is
900 DEG C are risen to 5 DEG C/min heating rate, and keeps the temperature 4 hours at 900 DEG C, so that said mixture initial reaction, forms
The garnet containing lithium of tetragonal phase.Then continue to be warming up to 1150 DEG C with the rate of 5 DEG C/min, and heat preservation 16 is small at such a temperature
When, be conducive to the formation of cubic phase and the stabilization procedures of cubic phase at this time.Subsequent furnace cooling takes out to room temperature and obtains mother
Powder.
Step 3: the female powder in step 2 is transferred in high energy ball mill, appropriate ball milling agent methyl methacrylate is added
Revolving speed 800r/min is arranged to whole female powders are covered in ester, and effective milling time is 40min.It is dried after ball milling.
Step 4: the product of step 3 kind is transferred in tube furnace, in an inert atmosphere, with the heating speed of 10 DEG C/min
Rate rises to 500 DEG C, and keeps the temperature 10 hours at 500 DEG C.This process purpose be by reduce carbon dioxide partial pressure,
To promote the decomposition of a small amount of lithium carbonate in female powder surface, the cubic phase stone powder of pomegranate containing lithium of higher purity is obtained.It is cooled to room
Wen Hou takes out product from tube furnace, obtains the electrolyte powder of garnet containing lithium of high-purity.
Embodiment 8
Step 1: being 20%, 45%, 20% and 15% successively to weigh lithium carbonate, lanthana, oxygen respectively according to mass fraction
Change zirconium and tantalum oxide, siccative is ground 90 minutes, when replacing wet-milling that can shorten the volatilization of wet-milling solvent to a certain extent using dry grinding
Between, improve production efficiency.
Step 2: above-mentioned mixture is placed in crucible with cover, it is sintered in Muffle furnace.The temperature of sintering is
900 DEG C are risen to 2 DEG C/min heating rate, and keeps the temperature 4 hours at 900 DEG C, so that said mixture initial reaction, forms
The garnet containing lithium of tetragonal phase.Then continue to be warming up to 1150 DEG C with the rate of 5 DEG C/min, and heat preservation 16 is small at such a temperature
When, be conducive to the formation of cubic phase and the stabilization procedures of cubic phase at this time.Subsequent furnace cooling takes out to room temperature and obtains mother
Powder.
Step 3: the female powder in step 2 is transferred in high energy ball mill, appropriate ball milling agent hexamethylene is added to covering
Whole female powders, are arranged revolving speed 1000r/min, and effective milling time is 10min.It is dried after ball milling.
Step 4: the product of step 3 kind is transferred in tube furnace, in an inert atmosphere, with the heating speed of 10 DEG C/min
Rate rises to 500 DEG C, and keeps the temperature 10 hours at 500 DEG C.This process purpose be by reduce carbon dioxide partial pressure,
To promote the decomposition of a small amount of lithium carbonate in female powder surface, the cubic phase stone powder of pomegranate containing lithium of higher purity is obtained.It is cooled to room
Wen Hou takes out product from tube furnace, obtains the electrolyte powder of garnet containing lithium of high-purity.
Claims (8)
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| EP3825282A4 (en) * | 2019-07-19 | 2021-11-17 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | CERAMIC POWDER MATERIAL, PROCESS FOR THE MANUFACTURING OF A CERAMIC POWDER MATERIAL AND BATTERY |
| CN113880577A (en) * | 2021-10-13 | 2022-01-04 | 上海交通大学 | Dry preparation process of solid electrolyte |
| WO2022222410A1 (en) * | 2021-04-23 | 2022-10-27 | 海南大学 | Solid electrolyte for lithium ion battery, and preparation method therefor |
| CN115548428A (en) * | 2022-11-30 | 2022-12-30 | 中自环保科技股份有限公司 | Preparation method of solid electrolyte with lithium carbonate on surface removed by reduced pressure roasting, battery solid electrolyte and solid battery |
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| WO2022222410A1 (en) * | 2021-04-23 | 2022-10-27 | 海南大学 | Solid electrolyte for lithium ion battery, and preparation method therefor |
| CN113880577A (en) * | 2021-10-13 | 2022-01-04 | 上海交通大学 | Dry preparation process of solid electrolyte |
| CN115548428A (en) * | 2022-11-30 | 2022-12-30 | 中自环保科技股份有限公司 | Preparation method of solid electrolyte with lithium carbonate on surface removed by reduced pressure roasting, battery solid electrolyte and solid battery |
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