CN105304938B - The electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium - Google Patents
The electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium Download PDFInfo
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- CN105304938B CN105304938B CN201510630965.3A CN201510630965A CN105304938B CN 105304938 B CN105304938 B CN 105304938B CN 201510630965 A CN201510630965 A CN 201510630965A CN 105304938 B CN105304938 B CN 105304938B
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- lithium
- titanium
- solid electrolyte
- phosphate aluminium
- aluminium lithium
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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
- H01M2300/0085—Immobilising or gelification of electrolyte
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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 relates to technical field of lithium ion, a kind of electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium is particularly disclosed.The electrochemical preparation method, the mixture of aluminum oxide and titanium dioxide is prepared according to al-ti ratio example first, then titanium dioxide is made to be embedded in lithium ion by electrochemical method, adding microcosmic salt further according to lithium aluminium titanium phosphorus ratio forms uniform mixture, and annealing obtains LATP solid electrolytes.Raw material of the present invention is cheap, technique is simple, it is the titanium phosphate aluminium lithium that can obtain high-purity by two steps of electrochemistry and high-temperature process, lithium aluminium titanium phosphorus ratio can be accurately controlled, solving the volatilization of lithium salts at high temperature in usual solid phase method causes the problem of product purity is relatively low.
Description
（One）Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of electrochemistry of solid electrolyte titanium phosphate aluminium lithium
Preparation method.
（Two）Background technology
The popularization of new-energy automobile can reduce environmental pollution, and wherein electrokinetic cell is key factor, and electrokinetic cell is usual
From liquid electrolyte, on fire or blast may be caused in abuse conditions, there is potential safety hazard.Use the complete of solid electrolyte
Solid state battery is greatly improved without using incendive liquid electrolyte, security, while the charge capacity of all-solid-state battery is more, defeated
Go out power also bigger, but the low ionic conductivity of solid electrolyte hinders the practicality of all-solid-state battery.
In solid electrolyte, titanium phosphate aluminium lithium Li1+xAlxTi2-x(PO4)3（LATP）Conductivity at room temperature is up to 10-3S/
Cm, particularly attracts people's attention close to business level of electrolyte.The method of synthesis titanium phosphate aluminium lithium common at present mainly includes solid
Phase method and sol-gal process, solid phase method technique are simple, but long-time high-temperature calcination causes energy consumption higher, and because lithium salts is in high temperature
Lower volatilization causes product purity relatively low, and sol-gal process is using expensive alkoxide, and cost is very high, is only suitable for laboratory research.
（Three）The content of the invention
There is provided a kind of control of ratio is accurate, product purity is high, can advise greatly in order to make up the deficiencies in the prior art by the present invention
The electrochemical preparation method of the solid electrolyte titanium phosphate aluminium lithium of mould production.
The present invention is achieved through the following technical solutions：
A kind of electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium, with titanium dioxide and aluminum oxide, binding agent and
Conductive agent is raw material, is comprised the following steps：
（1）Above-mentioned raw materials are well mixed, it is tabletted；
（2）By step（1）The piece of middle compacting is positive pole, and lithium piece is that negative pole is assembled into battery, according to the quality of titanium dioxide
The electricity that embedding lithium needs is calculated with the ratio of lithium titanium, is discharged on electric discharge instrument；
（3）After discharge off, the positive pole of embedding lithium is taken out, microcosmic salt is added and is well mixed, the high temperature anneal obtains titanium phosphate
Aluminium lithium.
The present invention more excellent technical scheme be：
The titanium dioxide is the nano particle that size is 25nm；Bulky grain adds the difficulty of Lithium-ion embeding, may
Cause embedding lithium uneven, reduce purity, short grained cost is higher, operating difficulties, 25nm titanium dioxide granule be at present into
Ripe commercial materials, are the optimal sizes of combination property.
Step（1）In, the binding agent is Kynoar or polytetrafluoroethylene (PTFE), and conductive agent is acetylene black and Super P
One or both of mixture；Binding agent ensure that the intensity of tabletting, but can influence electric conductivity and the increase of tabletting too much
Cost, does not have cementation, mass fraction is that 5-20% is optimal proportion, wherein it is preferred that 10% very little.Conductive agent ensure that pressure
Electric conductivity of the piece in discharge process, but the difficulty of film-making can be influenceed too much and increase cost, act on very little not substantially, quality point
Number is optimal proportion for 5-20%, wherein it is preferred that 10%.
Step（1）In, the mixed method of the raw material is ball-milling method or polishing.
Step（2）In, the battery is button cell, and electric discharge instrument is cell tester or electrochemical workstation；Full
The cell tester of lower range is selected under conditions of enough journeys as far as possible, discharge current is controlled in below 0.1C, it is ensured that lithium ion can
To be uniformly embedded into titanium dioxide.
Step（2）In, the discharge capacity is the embedding lithium needs calculated according to the quality of titanium dioxide and the ratio of lithium titanium
Electricity, titanium phosphate aluminium lithium Li1+xAlxTi2-x(PO4)3Middle lithium titanium mol ratio is（1+x）:（2-x）, then certain mass titanium dioxide
The calculation formula of electricity required for embedded corresponding amount lithium is,MAh, wherein m
For the grams of titanium dioxide, M is the molecular weight of titanium dioxide, and the lithium-inserting amount for discharging into now titanium dioxide meets titanium phosphate just
The mol ratio of aluminium lithium.
Step（3）In, titanium, the mol ratio of phosphorus are in microcosmic salt and titanium dioxide（2-x）：3, wherein, 0 ＜ x≤1, titanium phosphate
Aluminium lithium Li1+xAlxTi2-x(PO4)3There is the compound of a variety of different proportions, lithium, aluminium, titanium, the mol ratio of phosphorus are according to final product
Ratio-dependent；Microcosmic salt is red phosphorus, white phosphorus, black phosphorus, phosphorus pentoxide, diphosphorus trioxide, ammonium dihydrogen phosphate and diammonium hydrogen phosphate
In one or more；Some of which cost of material is more expensive, the easy moisture absorption of some raw materials, and preferably cheap performance is stable
Ammonium dihydrogen phosphate.
Step（3）In, the high annealing is divided into pre-burning and two stages of sintering, and the temperature of pre-burning is 500-850 DEG C, excellent
700 DEG C are selected, the temperature of sintering is 700-1100 DEG C, and the temperature preferably sintered is 900 DEG C；Pre-burning can ensure to remove in material
Binding agent, conductive agent and other impurities and the gas for decomposing generation.The sintering of higher temperature can ensure abundant reaction, and generation is brilliant
The controllable titanium phosphate aluminium lithium of grain.
Raw material of the present invention is cheap, technique simple, is that can obtain high-purity by two steps of electrochemistry and high-temperature process
Titanium phosphate aluminium lithium, can accurately control lithium aluminium titanium phosphorus ratio, and solving the volatilization of lithium salts at high temperature in usual solid phase method causes
The problem of product purity is relatively low.
（Four）Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is Li prepared by the embodiment of the present invention 11.3Al0.3Ti1.7(PO4)3XRD.
（Five）Embodiment
The present invention is described in further detail below by specific embodiment, but these embodiments are only that citing
Illustrate, the scope of the present invention is not defined.
Embodiment 1：
Weigh grinding half in 0.719g titanium dioxide, 0.081g aluminum oxide, 0.1g PVDF and 0.1g acetylene blacks, mortar small
When, is sufficiently mixed uniform, takes 0.2g mixtures to be put under mould, 20MPa pressure and suppresses 1 minute in flakes.Positive pole is done into tabletting, selected
With CR2032 button cell shells, electricity is assembled according to the order of negative electrode casing, spring leaf, pad, lithium piece, barrier film, positive pole, anode cover
Pond, is added dropwise 5 and drips lithium-ion battery electrolytes, button cell is prepared with sealing machine sealing.The button cell of preparation is put into battery
On tester, the capacity of 0.05C constant-current discharges to 36.84mAh.The tabletting after embedding lithium is taken out, with 0.365g di(2-ethylhexyl)phosphates after drying
700 DEG C of pre-burnings 10 hours in hydrogen ammonium ground and mixed, Muffle furnace, after grinding 900 DEG C again sintering obtain Li within 4 hours1.3Al0.3Ti1.7
(PO4)3。
Embodiment 2：
8.09g titanium dioxide, 0.91g aluminum oxide, 0.5g PVDF and 0.5g Super P are weighed, 100ml ball millings are put into
Tank, ratio of grinding media to material is 3:1, grinding is sufficiently mixed uniformly for 2 hours, is taken 0.2g mixtures to be put under mould, 20MPa pressure and is suppressed 1 point
Clock is in blocks.Positive pole is done into tabletting, from CR2032 button cell shells, according to negative electrode casing, spring leaf, pad, lithium piece, barrier film, just
Pole, the order assembled battery of anode cover, are added dropwise 5 and drip lithium-ion battery electrolytes, button cell is prepared with sealing machine sealing.Will system
Standby button cell is put on cell tester, the capacity of 0.05C constant-current discharges to 41.45mAh.The tabletting after embedding lithium is taken out,
With 0.41g ammonium dihydrogen phosphate ground and mixeds after drying, 550 DEG C of pre-burnings 10 hours in Muffle furnace, 1100 DEG C sinter 4 again after grinding
Hour obtains Li1.3Al0.3Ti1.7(PO4)3。
Claims (10)
1. a kind of electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium, with titanium dioxide and aluminum oxide, binding agent and lead
Electric agent is raw material, it is characterized in that, comprise the following steps：（1）Above-mentioned raw materials are well mixed, it is tabletted；（2）By step（1）
The piece of middle compacting is positive pole, and lithium piece is that negative pole is assembled into battery, and embedding lithium is calculated according to the quality of titanium dioxide and the ratio of lithium titanium
The electricity needed, discharges on electric discharge instrument；（3）After discharge off, the positive pole of embedding lithium is taken out, microcosmic salt is added and is well mixed, it is high
Temperature annealing obtains titanium phosphate aluminium lithium.
2. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, it is characterised in that：It is described
Titanium dioxide is the nano particle that size is 25nm.
3. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, it is characterised in that：Step
（1）In, the mixed method of the raw material is polishing；Binding agent is Kynoar or polytetrafluoroethylene (PTFE), accounts for raw material gross mass
5-20%, conductive agent be one or both of acetylene black and Super P mixture, account for the 5-20% of raw material gross mass.
4. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, it is characterised in that：Step
（2）In, the battery is button cell, and electric discharge instrument is cell tester or electrochemical workstation.
5. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, it is characterised in that：Step（2）
In, discharge capacity is the electricity that the embedding lithium calculated according to the quality of titanium dioxide and the ratio of lithium titanium needs, titanium phosphate aluminium lithium Li1+ xAlxTi2-x(PO4)3Middle lithium titanium mol ratio is（1+x）:（2-x）；The calculation formula of electricity is,MAh,
Wherein m is the grams of titanium dioxide, and M is the molecular weight of titanium dioxide, and the lithium-inserting amount for discharging into now titanium dioxide is met just
The mol ratio of titanium phosphate aluminium lithium.
6. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, it is characterised in that：Step
（3）In, titanium, the mol ratio of phosphorus are in microcosmic salt and titanium dioxide（2-x）：3, wherein, 0 ＜ x≤1；Microcosmic salt is red phosphorus, white phosphorus, black
One or more in phosphorus, phosphorus pentoxide, diphosphorus trioxide, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
7. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, it is characterised in that：Step
（3）In, the high annealing is divided into pre-burning and two stages of sintering, and the temperature of pre-burning is 500-850 DEG C, and the temperature of sintering is
700-1100℃。
8. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 4, it is characterised in that：Step
（2）In, electric discharge instrument is cell tester, and discharge current is controlled in below 0.1C.
9. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 6, it is characterised in that：Step
（3）In, microcosmic salt is ammonium dihydrogen phosphate.
10. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 7, it is characterised in that：Step
Suddenly（3）In, the temperature of the pre-burning is 700 DEG C, and the temperature of sintering is 900 DEG C.
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| US10033066B2 (en) * | 2016-02-29 | 2018-07-24 | Suzuki Motor Corporation | Solid electrolyte and method of manufacturing solid electrolyte |
| CN108336398B (en) * | 2018-03-26 | 2020-12-25 | 湘潭大学 | Inorganic/organic polymer composite solid electrolyte film and preparation method thereof |
| CN113451586A (en) * | 2021-05-27 | 2021-09-28 | 天津国安盟固利新材料科技股份有限公司 | Electrode plate of secondary battery, secondary battery and preparation method of secondary battery |
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| US10411288B2 (en) * | 2011-11-29 | 2019-09-10 | Corning Incorporated | Reactive sintering of ceramic lithium-ion solid electrolytes |
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