CN109065946A - A kind of method for preparing solid electrolyte - Google Patents
A kind of method for preparing solid electrolyte Download PDFInfo
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- CN109065946A CN109065946A CN201811080709.1A CN201811080709A CN109065946A CN 109065946 A CN109065946 A CN 109065946A CN 201811080709 A CN201811080709 A CN 201811080709A CN 109065946 A CN109065946 A CN 109065946A
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- solid electrolyte
- preparing solid
- electrolyte according
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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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses preparation method described in a kind of method for preparing solid electrolyte comprising steps of (1) weighs lithium salts, zirconates and phosphate by required stoichiometric ratio, is uniformly mixed；(2) by mixture after mixing, microwave pre-burning 2-6 hours at 400-800 DEG C；(3) tabletting after the mixture grinding uniformly after pre-burning is obtained into LiZr then microwave sintering 2-6 hours at 800-1000 DEG C2(PO4)3Solid electrolyte.Compared with prior art, sintering temperature of the present invention is low, with short production cycle, can obtain diamond structure LiZr stable at room temperature2(PO4)3, ionic conductance is up to 1.0 × 10 under room temperature‑6~8.0 × 10‑5S/cm。
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of method for preparing solid electrolyte.
Background technique
Lithium ion battery have energy density height, output power, voltage height, self discharge is small, operating temperature range is wide, nothing
Memory effect and advantages of environment protection have been applied to the fields such as electric vehicle, rail traffic, extensive energy storage and aerospace.
Currently, commercialized lithium ion battery uses liquid organic electrolyte, the electrolyte and electrode material hold in charge and discharge process
Side reaction easily occurs, causes battery capacity irreversible decaying occur, while battery, during long service, organic liquid is electrolysed
Phenomena such as matter will appear volatilization, dry up, reveal, influence battery life.On the other hand, conventional lithium ion battery is not available high energy
The lithium metal of metric density is as negative electrode material, in circulating battery, since metallic lithium surface current density and lithium ion are distributed not
Factors, the metal lithium electrode such as uniform dissolve repeatedly, deposit non-uniform hole and dendrite easy to form.Dendrite can pierce through diaphragm,
It reaches anode and causes a series of security risks such as battery short circuit, thermal runaway, Fire explosion.Liquid is replaced with solid electrolyte
Electrolyte is the fundamental way for obtaining the solid lithium battery of high-energy density, safety and long circulation life.
Commercial NASICON solid electrolyte Li in the market1.3Al0.3Ti1.7(PO4)3, lithium ion conductivity is in σLi>10- 4S/cm, and when doing electrode using lithium metal, Ti4+It is reduced into Ti3+, limit Li1.3Al0.3Ti1.7(PO4)3Use model
It encloses.And to LiZr2(PO4)3Solid electrolyte, due to the stability of zirconium ion and phosphonium ion, LiZr2(PO4)3The meeting in lithium battery
It is a relatively good selection, but LiZr2(PO4)3It is at room temperature three monoclinic phases, ionic conductivity 10-8S/cm；50 DEG C with
On, LiZr2(PO4)3It is transformed into rhombohedral phase, ionic conductivity 10-5S/cm, how stable lithium-ion electrolyte LiZr2(PO4)3
Keep rhombohedral phase will be very significant at room temperature.
Summary of the invention
The main purpose of the present invention is to provide a kind of all-solid lithium-ion battery method for preparing solid electrolyte, it is intended to
Solve the LiZr of existing method preparation2(PO4)3The problem of rhombohedral phase can not be stabilized at room temperature.
To achieve the above object, a kind of method for preparing solid electrolyte provided by the invention the following steps are included:
(1) lithium salts, zirconates and phosphate are weighed by required stoichiometric ratio, be uniformly mixed；
(2) by mixture after mixing, microwave pre-burning 2-6 hours at 400-800 DEG C；
(3) by tabletting after the mixture grinding uniformly after pre-burning, then microwave sintering 2-6 hours at 800-1000 DEG C,
Obtain LiZr2(PO4)3Solid electrolyte.
Preferably, the stoichiometric ratio in the step (1) is Li+:Zr4+:PO4 3-=1:1.5-2.5:2.5-3.5.
Preferably, the lithium salts in the step (1) includes one of lithium nitrate, lithium carbonate, lithium hydroxide and lithia
Or it is several.
Preferably, the zirconates in the step (1) includes one or more of zirconium nitrate, zirconium oxide.
Preferably, the phosphate in the step (1) includes ammonium dihydrogen phosphate, diammonium hydrogen phosphate, in hydrogen phosphite ammonium
It is one or more of.
Preferably, be additionally added doped metal salt in the step (1), doping metals include in Ca, Al, Sr, Ba, Y extremely
Few one kind, the step (3) obtain LixMyZrz(PO4)3Solid electrolyte, wherein [1,2] x, y, z ∈.
Preferably, be uniformly mixed in the step (1) is using ball milling method, with isopropanol, ethyl alcohol, acetone, n-butanol
One or more of be ball milling agent, using zirconium oxide tank and zirconia ball, rotational speed of ball-mill 100-1200rpm, ball milling 1-24 is small
When.
Preferably, temperature is risen to 400-800 DEG C with the heating rate of 5-40 DEG C/min in the step (2).
Preferably, tabletting is after grinding uniformly using agate mortar, to utilize press machine after the grinding of the step (3) uniformly
Product after compacting grinding, the pressure of press machine are 50-200Mpa, dwell time 1-30min.
Preferably, temperature is risen to 800-1000 DEG C with the heating rate of 5-40 DEG C/min in the step (3).
Compared with the prior art, technical solution of the present invention bring has the beneficial effect that:
(1) present invention can be obtained in room in the interior sintering of (800-1000 DEG C) short time at low temperature using Microwave Sintering Techniques
The LiZr of stable rhombohedral phase under temperature2(PO4)3Solid electrolyte, ionic conductance is up to 1.0 × 10 under room temperature-6~8.0 × 10- 5S/cm；
(2) after adulterating, the Li of the rhombohedral phase of acquisitionxMyZrz(PO4)3The ionic conductivity of solid electrolyte is higher, and
Compared with undoping, the temperature of sintering is lower, and the production cycle is shorter.
Detailed description of the invention
Fig. 1 is the pictorial diagram of solid electrolyte sheet made from embodiment 1；
Fig. 2 is the LiZr tested at room temperature after being sintered in embodiment 12(PO4)3XRD diagram and conventional sintering come out
LiZr2(PO4)3XRD diagram；
Fig. 3 is the impedance diagram that solid electrolyte sheet made from embodiment 1 measures at room temperature.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
The specific embodiment stated is used only for explaining the present invention rather than limiting the invention.
Embodiment 1:
2N pure reagent Li is weighed by required stoichiometric ratio2CO3、ZrO2And NH4H2PO4, the ball of zirconium oxide is put into after mixing
Grinding jar uses ethyl alcohol for ball milling agent, zirconia ball ball milling, rotational speed of ball-mill 400rpm, after 3 hours of ball milling, can be obtained after drying
Uniformly mixed raw material.
Raw material is placed in microwave equipment, 800 DEG C is warming up to the rate of 10 DEG C/min, 6h is kept the temperature, by gained powder
It is suppressed under 200Mpa pressure, obtained solid electrolyte sheet is placed in microwave equipment by pressure maintaining 10min, with the speed of 10 DEG C/min
Rate is warming up to 800 DEG C, and heat preservation 6h forms fine and close electrolyte sheet, obtains solid electrolyte after cooling, as shown in Figure 1.
Referring to figure 2., it is nethermost be rhombohedral phase standard card, the LiZr that this method is sintered out2(PO4)3In room temperature
It is down stable rhombohedral phase, and the LiZr that conventional sintering method obtains2(PO4)3It is at room temperature three oblique crystalline forms.
Referring to figure 3., pass through ionic conductivity calculation formula: σ=L/ (A × Z), unit S/cm；Wherein, L is thickness
(0.3cm), A are area (1.34cm2), Z is impedance (60K Ω), calculates the lithium electricity electricity for obtaining the solid electrolyte sheet at room temperature
Conductance σ=0.3/ (1.34 × 60000)=3.7 × 10-6S cm-1。
Embodiment 2:
Lithia, zirconium oxide and diammonium hydrogen phosphate are weighed by required stoichiometric ratio, the ball milling of zirconium oxide is put into after mixing
Tank uses isopropanol for ball milling agent, zirconia ball ball milling, rotational speed of ball-mill 100rpm, after 24 hours of ball milling, can be obtained after drying
Uniformly mixed raw material.Raw material is placed in microwave equipment, is warming up to 400 DEG C with the rate of 5 DEG C/min, keeps the temperature 6h, it is cooling
Gained powder is suppressed under 200Mpa pressure afterwards, and obtained solid electrolyte sheet is placed in microwave equipment, with 20 by pressure maintaining 10min
DEG C/rate of min is warming up to 1000 DEG C, 2h is kept the temperature, obtains solid electrolyte sheet after furnace cooling.The solid electrolyte at room temperature
The lithium electricity conductivity of piece is 7.4 × 10-5S cm-1。
Embodiment 3:
Lithium hydroxide, zirconium oxide and hydrogen phosphite ammonium are weighed by required stoichiometric ratio, the ball of zirconium oxide is put into after mixing
Grinding jar uses isopropanol for ball milling agent, zirconia ball ball milling, rotational speed of ball-mill 1200rpm, after 1 hour of ball milling, can obtain after drying
To uniformly mixed raw material.Raw material is placed in microwave equipment, is warming up to 600 DEG C with the rate of 30 DEG C/min, keeps the temperature 2h, it is cold
But gained powder is suppressed under 50Mpa pressure after, and obtained solid electrolyte sheet is placed in microwave equipment, with 30 by pressure maintaining 30min
DEG C/rate of min is warming up to 900 DEG C, 4h is kept the temperature, obtains solid electrolyte sheet after furnace cooling.The solid electrolyte at room temperature
The lithium electricity conductivity of piece is 8.4 × 10-6S cm-1。
Embodiment 4:
Lithium hydroxide, zirconium oxide, calcium carbonate and hydrogen phosphite ammonium are weighed by required stoichiometric ratio, oxidation is put into after mixing
The ball grinder of zirconium uses isopropanol for ball milling agent, zirconia ball ball milling, rotational speed of ball-mill 1000rpm, after 1.5 hours of ball milling, dries
Uniformly mixed raw material can be obtained after dry.Raw material is placed in microwave equipment, is warming up to 450 DEG C with the rate of 10 DEG C/min,
3h is kept the temperature, gained powder is suppressed under 100Mpa pressure after cooling, and obtained solid electrolyte sheet is placed in microwave by pressure maintaining 20min
In equipment, 850 DEG C are warming up to the rate of 10 DEG C/min, 3h is kept the temperature, obtains solid electrolyte sheet after furnace cooling.At room temperature should
The lithium electricity conductivity of solid electrolyte sheet is 2 × 10-4S cm-1。
Embodiment 5:
Lithium hydroxide, zirconium oxide, aluminium oxide and hydrogen phosphite ammonium are weighed by required stoichiometric ratio, oxidation is put into after mixing
The ball grinder of zirconium uses isopropanol for ball milling agent, zirconia ball ball milling, rotational speed of ball-mill 1000rpm, after 2 hours of ball milling, drying
Uniformly mixed raw material can be obtained afterwards.Raw material is placed in microwave equipment, 500 DEG C is warming up to the rate of 10 DEG C/min, protects
Warm 2.5h, gained powder is suppressed under 100Mpa pressure after cooling, and obtained solid electrolyte sheet is placed in microwave by pressure maintaining 20min
In equipment, 900 DEG C are warming up to the rate of 10 DEG C/min, 2.5h is kept the temperature, obtains solid electrolyte sheet after furnace cooling.At room temperature
The lithium electricity conductivity of the solid electrolyte sheet is 1.5 × 10-4S cm-1。
Claims (10)
1. a kind of method for preparing solid electrolyte, which is characterized in that the preparation method comprises the following steps:
(1) lithium salts, zirconates and phosphate are weighed by required stoichiometric ratio, be uniformly mixed；
(2) by mixture after mixing, microwave pre-burning 2-6 hours at 400-800 DEG C；
(3) tabletting after the mixture grinding uniformly after pre-burning is obtained then microwave sintering 2-6 hours at 800-1000 DEG C
LiZr2(PO4)3Solid electrolyte.
2. method for preparing solid electrolyte according to claim 1, which is characterized in that the chemistry meter in the step (1)
Amount is than being Li+:Zr4+:PO4 3-=1:1.5-2.5:2.5-3.5.
3. method for preparing solid electrolyte according to claim 1, which is characterized in that the lithium salts packet in the step (1)
Include one or more of lithium nitrate, lithium carbonate, lithium hydroxide and lithia.
4. method for preparing solid electrolyte according to claim 1, which is characterized in that the zirconates packet in the step (1)
Include one or more of zirconium nitrate, zirconium oxide.
5. method for preparing solid electrolyte according to claim 1, which is characterized in that the phosphate in the step (1)
Including one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, hydrogen phosphite ammonium.
6. method for preparing solid electrolyte according to claim 1, which is characterized in that be additionally added and mix in the step (1)
Miscellaneous metal salt, doping metals include at least one of Ca, Al, Sr, Ba, Y, and the step (3) obtains LixMyZrz(PO4)3Gu
Body electrolyte, wherein [1,2] x, y, z ∈.
7. any one of -6 method for preparing solid electrolyte according to claim 1, which is characterized in that in the step (1)
Be uniformly mixed is to use oxygen with one or more of isopropanol, ethyl alcohol, acetone, n-butanol for ball milling agent using ball milling method
Change zirconium tank and zirconia ball, rotational speed of ball-mill 100-1200rpm, ball milling 1-24 hours.
8. any one of -6 method for preparing solid electrolyte according to claim 1, which is characterized in that in the step (2)
Temperature is risen to 400-800 DEG C with the heating rate of 5-40 DEG C/min.
9. any one of -6 method for preparing solid electrolyte according to claim 1, which is characterized in that the step (3)
Tabletting is to utilize the product after press machine compacting grinding, the pressure of press machine after grinding uniformly using agate mortar after grinding uniformly
Power is 50-200Mpa, dwell time 1-30min.
10. method for preparing solid electrolyte according to claim 9, which is characterized in that with 5-40 in the step (3)
DEG C/temperature rises to 800-1000 DEG C by the heating rate of min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110994010A (en) * | 2019-12-31 | 2020-04-10 | 中兴高能技术有限责任公司 | Halide solid electrolyte, preparation method thereof and lithium ion battery |
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| CN108155413A (en) * | 2018-01-12 | 2018-06-12 | 北京科技大学 | The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method |
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Patent Citations (6)
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| JP2002110227A (en) * | 2000-09-29 | 2002-04-12 | National Institute For Materials Science | Method for manufacturing lithium ion conductive solid electrolyte thin film |
| WO2017197406A1 (en) * | 2016-05-13 | 2017-11-16 | Quantumscape Corporation | Solid electrolyte separator bonding agent |
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Effective date of registration: 20220623 Address after: 510555 room 690, room 406, No. 1, Yichuang street, Huangpu District, Guangzhou City, Guangdong Province (Zhongxin Guangzhou Knowledge City) Patentee after: Guangzhou Boyue New Material Technology Co.,Ltd. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: CENTRAL SOUTH University |