CN105206869B - A kind of electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide - Google Patents
A kind of electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide Download PDFInfo
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- CN105206869B CN105206869B CN201510620932.0A CN201510620932A CN105206869B CN 105206869 B CN105206869 B CN 105206869B CN 201510620932 A CN201510620932 A CN 201510620932A CN 105206869 B CN105206869 B CN 105206869B
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- H—ELECTRICITY
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
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- 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
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Abstract
The invention belongs to field of lithium ion battery, more particularly to a kind of electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide.The electrochemical preparation method of the solid electrolyte lithium lanthanum titanium oxide makes titanium dioxide be embedded in appropriate lithium ion by electrochemical method first, and then adding lanthanum salt according to Li-La-Ti ratio forms uniform mixture, and annealing obtains Ca-Ti ore type LLTO.The present invention is by controlling discharge electricity amount accurately to control the content of lithium, so as to obtain the lithium lanthanum titanium oxide of high-purity.The present invention can accurately control Li-La-Ti ratio, solving the volatilization of lithium salts at high temperature in usual solid phase method causes the problem of product purity is relatively low, raw material is cheap simultaneously, and technique is simple, and the lithium lanthanum titanium oxide of high-purity is can be obtained by by two steps of electrochemistry and high-temperature process.
Description
（One）Technical field
The invention belongs to field of lithium ion battery, more particularly to a kind of electrochemistry of solid electrolyte lithium lanthanum titanium oxide
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, perovskite structure compound lithium lanthanum titanium oxide Li3xLa2/3-xTiO3（LLTO）Room-temperature ion
Electrical conductivity is up to 10-3S/cm, particularly attracts people's attention close to business level of electrolyte.Synthesis Li-La-Ti oxidation common at present
The method of compound mainly includes solid phase method and sol-gal process, and solid phase method technique is simple, but long-time high-temperature calcination causes energy consumption
It is higher, and cause product purity relatively low because lithium salts volatilizees at high temperature, sol-gal process is using expensive alkoxide, and cost is very
Height, is only suitable for laboratory research.
（Three）The content of the invention
There is provided a kind of solid electrolyte rational in infrastructure, easy to use in order to make up the deficiencies in the prior art by the present invention
The electrochemical preparation method of lithium lanthanum titanium oxide.
The present invention is achieved through the following technical solutions：
A kind of electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide, includes following by raw material of titanium dioxide
Step：
（1）Raw material titanium dioxide, binding agent, conductive agent are well mixed, it is tabletted；
（2）With 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, the appropriate lanthanum salt of addition is well mixed, the high temperature anneal is obtained
Lithium lanthanum titanium oxide.
Step（1）In, titanium dioxide is nano particle, and granular size is 25nm, and bulky grain adds Lithium-ion embeding
Difficulty, it is uneven to be likely to result in embedding lithium, reduces purity, and short grained cost is higher, operating difficulties, 25nm titanium dioxide granule
It is current ripe commercial materials, is the optimal size of combination property.
Step（1）Described in binding agent be Kynoar, one kind of polytetrafluoroethylene (PTFE)；Conductive agent is acetylene black, Super
P one kind or mixture；Wherein, binding agent is the 5-20% of raw material gross mass, preferably 10%；Conductive agent is the 5- of raw material gross mass
20%, preferably 10%.Binding agent ensure that the intensity of tabletting, but can influence the electric conductivity of tabletting too much and increase cost, rise very little
Less than cementation, mass fraction is optimal proportion for 5~20%.Conductive agent ensure that electric conductivity of the tabletting in discharge process,
But the difficulty of film-making can be influenceed too much and increases cost, acted on very little not substantially, mass fraction is optimal proportion for 5~20%.
Step（1）The method of the mixing of the raw material includes ball-milling method and polishing.
Step（2）The battery is button cell.
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
Amount, lithium lanthanum titanium oxide Li3xLa2/3-xTiO3Middle lithium titanium mol ratio is 3x:1, then certain mass titanium dioxide insertion corresponding amount
Electricity calculation formula required for lithium is：MAh, wherein m are gram of titanium dioxide
Number, M is the molecular weight of titanium dioxide, discharges into the lithium-inserting amount of now titanium dioxide exactly 3x.
Step（2）In, described electric discharge instrument is cell tester or electrochemical workstation, under conditions of range is met
The cell tester of lower range is selected as far as possible, and discharge current is controlled in below 0.1C, it is ensured that lithium ion can be uniformly embedded into
In titanium dioxide.
Step（3）The lanthanum salt be lanthana, lanthanum hydroxide, lanthanum nitrate, lanthanum oxalate, one kind of lanthanum acetate or mixture,
Preferably lanthana.
Step（3）The lanthanum salt and the mol ratio of titanium dioxide are（2/3-x）：1, wherein, 0.06≤x≤1/6, Li-La-Ti
Oxygen compound Li3xLa2/3-xTiO3There is a compound of a variety of different proportions, the mol ratio of lanthanum and titanium is the ratio according to final product
It is determined that.
Step（3）The high annealing is divided into pre-burning and two stages of sintering, and the temperature of pre-burning is 500~850 DEG C, preferably
800℃；The temperature of sintering is 900~1200 DEG C, preferably 1000 DEG C.Pre-burning can ensure remove material in binding agent,
Conductive agent and other impurities and the gas for decomposing generation.The sintering of higher temperature can ensure abundant reaction, generate controllable crystal
Lithium lanthanum titanium oxide.
The beneficial effects of the invention are as follows：The present invention can accurately control Li-La-Ti ratio, solve lithium in usual solid phase method
The volatilization of salt at high temperature causes the problem of product purity is relatively low, while raw material is cheap, technique is simple, passes through electrochemistry and high temperature
Two steps of processing can be obtained by the lithium lanthanum titanium oxide of high-purity.
（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 10.33La0.557TiO3XRD.
Fig. 2 is Li prepared by the embodiment of the present invention 10.33La0.557TiO3AC impedance figure.
（Five）Embodiment
Embodiment 1
Weigh in 0.8g titanium dioxide, 0.1g PVDF and 0.1g acetylene blacks, mortar grind half an hour be sufficiently mixed uniformly,
Take 0.2g mixtures to be put under mould, 20MPa pressure and suppress 1 minute in flakes.Positive pole is done into tabletting, from CR2032 button cells
Shell, according to negative electrode casing, spring leaf, pad, lithium piece, barrier film, positive pole, anode cover order assembled battery, be added dropwise 5 drip lithium-ion electrics
Pond electrolyte, button cell is prepared with sealing machine sealing.The button cell of preparation is put on cell tester, 0.05C constant currents
It is discharged to 17.69mAh capacity.The tabletting after embedding lithium is taken out, with 0.181g lanthana ground and mixeds after drying, in Muffle furnace
800 DEG C of pre-burnings 5 hours, after grinding 1000 DEG C again sintering obtain Li within 10 hours0.33La0.557TiO3, testing conductivity after tabletting
For 3.8 × 10-4S/cm。
Embodiment 2
9g titanium dioxide, 0.5g PVDF and 0.5g Super P are weighed, 100ml ball grinders are put into, ratio of grinding media to material is 3:1, grind
Mill is sufficiently mixed uniformly for 2 hours, is taken 0.2g mixtures to be put under mould, 20MPa pressure and is suppressed 1 minute in flakes.Tabletting is done just
Pole, from CR2032 button cell shells, according to negative electrode casing, spring leaf, pad, lithium piece, barrier film, positive pole, anode cover order group
Packed battery, 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
On cell tester, the capacity of 0.05C constant-current discharges to 19.9mAh.The tabletting after embedding lithium is taken out, with 0.2042g oxygen after drying
Change lanthanum ground and mixed, 550 DEG C of pre-burnings 5 hours in Muffle furnace, after grinding 1200 DEG C again sintering obtain within 10 hours
Li0.33La0.557TiO3 。
Claims (10)
1. a kind of electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide, using titanium dioxide as raw material, its feature exists
In：Comprise the following steps：
（1）Raw material titanium dioxide, binding agent, conductive agent are well mixed, it is tabletted；
（2）With 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 and lithium of titanium dioxide
The ratio of titanium calculates the electricity that embedding lithium needs, and is discharged on electric discharge instrument；
（3）After discharge off, the positive pole of embedding lithium is taken out, the appropriate lanthanum salt of addition is well mixed, the high temperature anneal obtains lithium lanthanum
Titanium oxygen compound.
2. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterised in that：
Step（1）Described in titanium dioxide be nano particle, granular size is 25nm.
3. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterised in that：
Step（1）Described in binding agent be Kynoar, one kind of polytetrafluoroethylene (PTFE)；Conductive agent is acetylene black, Super P one kind
Or mixture；Wherein, binding agent is the 5-20% of raw material gross mass；Conductive agent is the 5-20% of raw material gross mass.
4. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterised in that：
Step（1）The method of the mixing of the raw material includes polishing.
5. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterised in that：
Step（2）The battery is button cell.
6. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide 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, Li-La-Ti
Oxygen compound Li3xLa2/3-xTiO3Middle lithium titanium mol ratio is 3x:1, then required for certain mass titanium dioxide insertion corresponding amount lithium
Electricity calculation formula be：MAh, wherein m are the grams of titanium dioxide, and M is the molecular weight of titanium dioxide, discharges into now two
The lithium-inserting amount of titanium oxide is exactly 3x.
7. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterised in that：
Step（2）In, electric discharge instrument is cell tester or electrochemical workstation, and discharge current is controlled in below 0.1C.
8. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterised in that：
Step（3）The lanthanum salt is lanthana, lanthanum hydroxide, lanthanum nitrate, lanthanum oxalate, one kind of lanthanum acetate or mixture.
9. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterised in that：
Step（3）The lanthanum salt and the mol ratio of titanium dioxide are（2/3-x）：1, wherein, 0.06≤x≤1/6.
10. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, its feature exists
In：Step（3）The high annealing is divided into pre-burning and two stages of sintering, and the temperature of pre-burning is 500~850 DEG C；The temperature of sintering
Spend for 900~1200 DEG C.
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| CN109390626B (en) * | 2017-08-08 | 2021-09-21 | 深圳格林德能源集团有限公司 | Inorganic solid electrolyte synthesis process and solid battery thereof |
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| CN100450933C (en) * | 2006-12-15 | 2009-01-14 | 清华大学 | Manufacture method of lithium lanthanum titanium oxide |
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