CN109103551A - lithium-air battery and its inorganic solid electrolyte and preparation method - Google Patents
lithium-air battery and its inorganic solid electrolyte and preparation method Download PDFInfo
- Publication number
- CN109103551A CN109103551A CN201810984540.6A CN201810984540A CN109103551A CN 109103551 A CN109103551 A CN 109103551A CN 201810984540 A CN201810984540 A CN 201810984540A CN 109103551 A CN109103551 A CN 109103551A
- Authority
- CN
- China
- Prior art keywords
- lithium
- air battery
- preparation
- ionic liquid
- tube furnace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The invention belongs to field of chemical power source more particularly to a kind of lithium-air battery and its inorganic solid electrolytes and preparation method.The electrolyte is to be made by a certain percentage by mechanical attrition method by lithia, phosphorus pentoxide and aluminum oxide and titanium dioxide, and electrolyte is Li1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3；Solid electrolyte is non-volatile, and component does not change；Moisture is not absorbed, is not reacted with electrode, therefore anode metal lithium can be effectively prevented and be corroded；Stability is preferable, and battery is allow to work at relatively high temperatures, improves the security performance of battery.It is greatly promoted the commercialized development of lithium-air battery.
Description
Technical field
The invention belongs to field of chemical power source more particularly to a kind of lithium-air battery and its inorganic solid electrolytes
With preparation method.
Background technique
Energy storage device is the key technology of modern humans' progress, the Novel electric of the development need high-energy-density of Future New Energy Source
Pond body system plays a role.High-energy-density metal-air battery can use the oxygen in air and be restored, and air is not in electricity
It is stored in pond, therefore the specific energy of battery can be substantially improved；Since lithium-air battery has operating voltage height, cycle life
Long, many advantages, such as environmental pollution is small, become the following Green Chemistry energy that pole is expected.Influencing its commercialized numerous mistake
The chemical property of Cheng Zhong, one side lithium-air battery anode metal lithium are active, so lithium-air battery cannot be directly using common
Water based electrolyte；On the other hand due to high-energy density lithium-air battery due to using organic electrolyte there are easy-to-leak liquid, kindling,
A series of security risks such as explosion promote battery security and become the emphasis to study instantly.Therefore it is more suitable to need to find
Electrolyte come solve the problems, such as there is currently.Solid electrolyte burning point is high at present, does not react with lithium metal, so peace
Entirely, and flexibility is good, and price is low, durable, ultra-thin, and stable solid-liquid-gas three-phase is easy to get during ORR and OER
Interface, it is more and more of interest by people.
Summary of the invention
Present invention aim to address the above problem present in the prior art, a kind of lithium-air battery and its nothing are provided
Machine solid electrolyte and preparation method.Electrolyte is prepared by mechanical attrition method in the present invention, is prepared using the electrolyte
Battery can work at relatively high temperatures, improve the security performance of battery.
The above problem of the invention is solved by following scheme:
A kind of lithium-air battery inorganic solid electrolyte, the electrolyte are Li1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3。
A kind of lithium-air battery inorganic solid electrolyte preparation method, which is characterized in that it is made by mechanical attrition method, point
Minor is Li1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3, it specifically includes:
Step 1 successively weighs the lithia that mass fraction is 99~99.5%, three oxidations that mass fraction is 95~98%
Two aluminium, the phosphorus pentoxide that the titanium dioxide and mass fraction that mass fraction is 99~99.8% are 99.99% is in clean
In agate mortar, the ratio between their amount of substance is respectively 6~8:14~17:2~3:30.30~60 are ground in the agate mortar
Minute, it is uniformly mixed solid；Then alcohol is added in the solid mixed, be placed in plastic bottle, zirconium oxide abrasive ball is added
Carry out ball milling.
The good raw material of ball milling described in step 1 is placed in 80 DEG C of baking oven by step 2, dries wherein remaining alcohol；It dries
Finish and being placed in porcelain crucible, and crucible is put into tube furnace, 800 DEG C constant temperature 5 hours, in the process constantly to pipe
It is passed through argon gas in formula furnace, reaction is taken away and decomposes the small molecules such as the carbon dioxide of release, it is then cooling, obtain Li1.3~1.6Ti1.4~ 1.7Al0.4~0.6(PO4)3Crude product.
Crude product described in step 2 is added in agate mortar and grinds 60 minutes by step 3, adds suitable alcohol, washs
Repeatedly, it is then centrifuged in centrifuge high speed, once takes 1~1.2g solid to be put into powder compressing machine centrifugation obtained solid and press
Piece, so that it is 18mm, the disk of thickness 2mm that a diameter, which is made,.
Step 4 carries out disk described in step 3 in tube furnace, and constant temperature 12 hours at 1000 DEG C are then naturally cold
But, Li is obtained immediately1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3Inorganic solid electrolyte piece.
As preferential, the rate that is passed through of argon gas is 2~3mL/ minutes in the step 2
As preferential, the alcohol of the step 2 is absolute alcohol
As preferential, the temperature programming of tube furnace is 2~3 DEG C/min in the step 2
As preferential, the revolving speed of centrifuge is in 8000~10000r/min in the step 3
As preferential, the temperature programming of tube furnace is 5~10 DEG C/min in the step 4
A kind of ionic liquid electrolyte is used for lithium-air battery, and wherein lithium-air battery includes cathode of lithium, air pole, electrolysis
Matter and seal casinghousing.
It is evidenced from the above discussion that solid electrolyte of the present invention is non-volatile, component does not change；Do not absorb moisture, not with
Electrode reacts, therefore anode metal lithium can be effectively prevented and be corroded；Stability is preferable, allows battery at relatively high temperatures
Work, improves the security performance of battery.It is greatly promoted the commercialized development of lithium-air battery.
Detailed description of the invention:
Attached drawing 1 is lithium-air battery schematic diagram.
Attached drawing 2 is the lithium-air battery structural schematic diagram after assembling.
Specific embodiment
The present invention provides a kind of lithium-air battery inorganic solid electrolytes and preparation method thereof, in order to make skill of the invention
Art scheme, purpose etc. is more clear, describes the invention in detail below.
The lithium-air battery inorganic solid electrolyte of the present embodiment is Li1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3.At room temperature
Ionic conductivity be up to 1.52 × 10-3S/cm, capacity reach 105 μ Ah/cm2μm。
The present embodiment additionally provides electrolyte preparation method, is particularly prepared by mechanical attrition method,
And the following steps are included:
Step 1: the lithia that mass fraction is 99~99.5%, three oxygen that mass fraction is 95~98% are successively weighed
Change two aluminium, the phosphorus pentoxide that the titanium dioxide and mass fraction that mass fraction is 99~99.8% are 99.99% is in clean
Agate mortar in, the ratio between their amount of substance be respectively 6~8:14~17:2~3:30.In the agate mortar grinding 30~
60 minutes, it is uniformly mixed solid；Then alcohol is added in the solid mixed, be placed in container, zirconium oxide abrasive ball is added
Carry out ball milling；
Step 2: the good raw material of ball milling described in step 1 is placed in 80 DEG C of baking oven, dries wherein remaining alcohol；
Dried and be placed in porcelain crucible, and crucible has been put into tube furnace, 800 DEG C constant temperature 5 hours, in the process constantly to
It is passed through protective gas in tube furnace, such as argon gas, nitrogen, takes away reaction and decomposes the small molecules such as the carbon dioxide of release, it is then cold
But, Li is obtained1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3Crude product；
Step 3:, will crude product described in step 2 be added agate mortar in grind 60 minutes, add suitable alcohol, wash
It washs repeatedly, is then centrifuged in centrifuge high speed, once take 1~1.2g solid to be put into powder compressing machine centrifugation obtained solid
Tabletting, so that it is 18mm, the disk of thickness 2mm that a diameter, which is made,；
Step 4: disk described in step 3 is carried out in tube furnace, constant temperature 12 hours at 1000 DEG C are then naturally cold
But, Li is obtained immediately1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3Inorganic solid electrolyte piece；
Wherein, the alcohol of the step 1 is absolute alcohol；Argon gas is passed through rate as 2~3mL/ points in the step 2
Clock；The temperature programming of step 2 tube furnace is 2~3 DEG C/min；The revolving speed of step 3 centrifuge is in 8000~10000r/
min.The temperature programming of step 4 tube furnace is 5~10 DEG C/min.
The present embodiment additionally provides the lithium-air battery using the electrolyte.Specially by inorganic solid electrolyte obtained
It is being placed between the cathode of lithium of lithium-air battery and air pole in glove box, lithium-air battery is assembled by sealing shell,
As shown in the figure 2.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (9)
1. a kind of lithium-air battery ionic liquid electrolyte, which is characterized in that molecular formula Li1.3~1.6Ti1.4~1.7Al0.4~0.6
(PO4)3。
2. a kind of preparation method of lithium-air battery ionic liquid electrolyte characterized by comprising
It is uniformly mixed it lithia, aluminum oxide, titanium dioxide, phosphorus pentoxide grinding, then consolidates what is mixed
Zirconium oxide abrasive ball progress ball milling is added after alcohol is added in body；
Alcohol is removed in the raw material good from ball milling, argon gas several hours are passed through under 800 DEG C of high temperature, reaction is taken away and decomposes release
Cooling obtains Li after carbon dioxide small molecule1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3Crude product.
3. a kind of preparation method of lithium-air battery ionic liquid electrolyte according to claim 2, which is characterized in that packet
It includes:
It grinds the crude product and is centrifuged with after ethanol wash in centrifuge high speed, centrifugation obtained solid is put into pressed powder
Tabletting in machine；
Cooling obtains the Li after tabletting is put into the processing of tube furnace high temperature1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3It is inorganic solid
Body electrolyte sheet.
4. a kind of preparation method of lithium-air battery ionic liquid electrolyte according to claim 2, which is characterized in that packet
Include: the lithia, aluminum oxide, titanium dioxide, phosphorus pentoxide mass ratio be 6~8:14~17:2~3:30.
5. a kind of preparation method of lithium-air battery ionic liquid electrolyte according to claim 2, which is characterized in that packet
It includes:
The good raw material of ball milling is placed in baking oven and dries residual alcohol；It has dried and has been put into tube furnace after being placed in porcelain crucible,
800 DEG C constant temperature 5 hours, argon gas is constantly passed through into tube furnace in the process, take away reaction decompose release carbon dioxide
Etc. small molecules, it is then cooling, obtain Li1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3Crude product.
6. a kind of preparation method of lithium-air battery ionic liquid electrolyte according to claim 2, which is characterized in that
The crude product is added in agate mortar and is ground 60 minutes, adds suitable alcohol, washing is multiple, then in centrifuge
Centrifugation obtained solid is once taken 1~1.2g solid to be put into tabletting in powder compressing machine by high speed centrifugation.
7. a kind of preparation method of lithium-air battery ionic liquid electrolyte according to claim 2, which is characterized in that will
Tabletting is put into tube furnace, and constant temperature 12 hours at 1000 DEG C, then natural cooling, obtains Li immediately1.3~1.6Ti1.4~ 1.7Al0.4~0.6(PO4)3Inorganic solid electrolyte piece.
8. a kind of preparation method of lithium-air battery ionic liquid electrolyte characterized by comprising
Step 1 takes lithia, and aluminum oxide, the phosphorus pentoxide that titanium dioxide and mass fraction are 99.99% is in clean
In agate mortar, the ratio between their amount of substance is respectively 6~8:14~17:2~3:30.30~60 are ground in the agate mortar
Minute, it is uniformly mixed solid；Then alcohol is added in the solid mixed, be placed in plastic bottle, zirconium oxide abrasive ball is added
Carry out ball milling；
The good raw material of ball milling described in step 1 is placed in baking oven by step 2, dries wherein remaining alcohol；Postposition is dried
Be put into tube furnace in porcelain crucible, and by crucible, 800 DEG C constant temperature 5 hours, in the process constantly into tube furnace lead to
Enter argon gas, takes away reaction and decompose the small molecules such as the carbon dioxide of release, it is then cooling, obtain Li1.3~1.6Ti1.4~1.7Al0.4~0.6
(PO4)3Crude product；
Crude product described in step 2 is added in agate mortar and grinds by step 3, adds suitable alcohol, washing is multiple, then
It is centrifuged in centrifuge high speed, once takes 1~1.2g solid to be put into tabletting in powder compressing machine centrifugation obtained solid, to make
Obtaining a diameter is 18mm, the disk of thickness 2mm；
Step 4 carries out disk described in step 3 in tube furnace, constant temperature 12 hours at 1000 DEG C, then natural cooling, with
Obtain Li1.3~1.6Ti1.4~1.7Al0.4~0.6(PO4)3Inorganic solid electrolyte piece.
9. a kind of lithium-air battery, which is characterized in that including electrolyte described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810984540.6A CN109103551A (en) | 2018-08-28 | 2018-08-28 | lithium-air battery and its inorganic solid electrolyte and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810984540.6A CN109103551A (en) | 2018-08-28 | 2018-08-28 | lithium-air battery and its inorganic solid electrolyte and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109103551A true CN109103551A (en) | 2018-12-28 |
Family
ID=64851578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810984540.6A Pending CN109103551A (en) | 2018-08-28 | 2018-08-28 | lithium-air battery and its inorganic solid electrolyte and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109103551A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335704A (en) * | 2021-12-27 | 2022-04-12 | 溧阳天目先导电池材料科技有限公司 | Preparation method and application of high-performance solid electrolyte slurry |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014078648A1 (en) * | 2012-11-15 | 2014-05-22 | Corning Incorporated | Solid ceramic electrolytes |
| CN106505248A (en) * | 2016-10-26 | 2017-03-15 | 中国地质大学（武汉） | A kind of glass ceramics type method for preparing solid electrolyte |
-
2018
- 2018-08-28 CN CN201810984540.6A patent/CN109103551A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014078648A1 (en) * | 2012-11-15 | 2014-05-22 | Corning Incorporated | Solid ceramic electrolytes |
| CN106505248A (en) * | 2016-10-26 | 2017-03-15 | 中国地质大学（武汉） | A kind of glass ceramics type method for preparing solid electrolyte |
Non-Patent Citations (2)
| Title |
|---|
| HIDEYUKI MORIMOTO, HIROYUKI AWANO等: "Preparation of lithium ion conducting solid electrolyte of NASICON-type Li1+xAlxTi2-x(PO4)3 (x =0.3) obtained by using the mechanochemical method and its application as surface modification materials of LiCoO2 cat", 《JOURNAL OF POWER SOURCES》 * |
| 盛超宇，黄哲，邵慧萍，郑航: "锂空气电池固体电解质Li1+xAlxTi2-x(PO4)3的制备研究", 《粉末冶金工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335704A (en) * | 2021-12-27 | 2022-04-12 | 溧阳天目先导电池材料科技有限公司 | Preparation method and application of high-performance solid electrolyte slurry |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2943111T3 (en) | Solid inorganic sulfide electrolyte with high air stability, and method of preparation and use thereof | |
| CN106505248A (en) | A kind of glass ceramics type method for preparing solid electrolyte | |
| CN103496740B (en) | Electric field activated sintering method of solid electrolyte material | |
| CN106252624B (en) | Cathode of lithium battery poriferous titanium dioxide and preparation method thereof | |
| CN108390094B (en) | Air-stable sulfide sodium ion solid electrolyte and preparation method thereof | |
| CN102683744A (en) | Rechargeable magnesium battery taking oxygen-containing organic matter as cathode material, and preparation method thereof | |
| CN105810920A (en) | Preparation method of negative electrode material of organic system sodium-ion battery | |
| CN108899521A (en) | Utilize waste silicon powder and the compound method for preparing ion cathode material lithium of carbon | |
| CN106328946A (en) | Method for preparing nano-micro carbon-sulfur composite by in-situ carbon coating of sulfur | |
| CN109192981A (en) | A kind of three nickel positive electrode of foam curing and the preparation method and application thereof | |
| CN106711437A (en) | Production method of low-cost and high-capacity all-solid-state lithium ion battery | |
| CN102867947A (en) | Method for preparing carbon/silicon composite anode material based on oligomeric silsesquioxane | |
| CN112777632A (en) | Sulfide lithium ion solid electrolyte and preparation method and application thereof | |
| CN109285983A (en) | Using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof | |
| CN106115785B (en) | A kind of pure phase MoO2Anode material of lithium-ion battery and preparation method thereof | |
| CN113937351A (en) | Geranite type sulfide lithium ion solid electrolyte and preparation method and application thereof | |
| CN109037552A (en) | A kind of preparation method of the diaphragm material for sodium-sulphur battery | |
| CN107681194A (en) | A kind of oxygen doping inorganic sulphide solid electrolyte and preparation method thereof | |
| CN110112459B (en) | Preparation method of sulfide solid electrolyte and all-solid-state lithium-sulfur battery | |
| CN105810901A (en) | Ti<3+>/Ti<4+> mixed-valence lithium titanate negative electrode material doped with iron element and preparation of negative electrode material | |
| CN103378355A (en) | Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance | |
| CN105047870A (en) | Nitrogen-doped carbon-coated silicon composite material and preparation method thereof | |
| CN109103551A (en) | lithium-air battery and its inorganic solid electrolyte and preparation method | |
| CN109713259A (en) | A kind of silicon-carbon composite cathode material of lithium ion battery and its preparation method and application | |
| CN112225196A (en) | Method for preparing carbon-based negative electrode material from ester bond-rich waste plastic and application of carbon-based negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181228 |
|
| RJ01 | Rejection of invention patent application after publication |