CN105206869A - Method for electrochemically preparing solid electrolyte lithium lanthanum titanium oxides - Google Patents

Method for electrochemically preparing solid electrolyte lithium lanthanum titanium oxides Download PDF

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Publication number
CN105206869A
CN105206869A CN201510620932.0A CN201510620932A CN105206869A CN 105206869 A CN105206869 A CN 105206869A CN 201510620932 A CN201510620932 A CN 201510620932A CN 105206869 A CN105206869 A CN 105206869A
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Prior art keywords
lithium
lanthanum
solid electrolyte
titanium oxide
lithium lanthanum
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CN201510620932.0A
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CN105206869B (en
Inventor
张庆朋
赵成龙
李丽
王瑛
于文倩
王超武
陈建伟
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Shandong Yuhuang Chemical Co Ltd
Shandong Yuhuang New Energy Technology Co Ltd
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Shandong Yuhuang Chemical Co Ltd
Shandong Yuhuang New Energy Technology Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • H01M2300/0071—Oxides
    • 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 invention belongs to the field of lithium ion batteries, particularly relates to a method for electrochemically preparing solid electrolyte lithium lanthanum titanium oxides, wherein a moderate amount of lithium ions are embedded into titanium dioxide, then lanthanum salts are added to form uniform mixtures according to the ratio of lithium lanthanum titanium, thereby obtaining perovskite type lithium lanthanum titanate (LLTO) by annealing. The method for electrochemically preparing the solid electrolyte lithium lanthanum titanium oxides can accurately control content of lithium by controlling discharge electric quantity, thereby being capable of obtaining high-purity lithium lanthanum titanium oxides. The method for electrochemically preparing the solid electrolyte lithium lanthanum titanium oxides can accurately control radio of lithium lanthanum titanium, solves the problem that lithium salts are volatilized in high temperature to cause the purity of products to be lower in a common solid phase method, is cheap in raw materials simultaneously and simple in process, and can obtain high-purity lithium lanthanum titanium oxides through two steps of electrochemistry and high temperature treatment.

Description

A kind of electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide
(1) technical field
The invention belongs to field of lithium ion battery, particularly a kind of electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide.
(2) background technology
The universal of new-energy automobile can reduce environmental pollution, and wherein electrokinetic cell is key factor, and electrokinetic cell selects liquid electrolyte usually, may cause on fire or blast in abuse conditions, there is potential safety hazard.Use the all-solid-state battery of solid electrolyte not use incendive liquid electrolyte, fail safe significantly improves, and the charge capacity of all-solid-state battery is more simultaneously, power output is also larger, 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 Li 3xla 2/3-xtiO 3(LLTO) 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 lithium lanthanum titanium oxide common at present mainly comprises solid phase method and sol-gal process, solid phase method technique is simple, but long-time high-temperature calcination causes energy consumption higher, and cause product purity lower because lithium salts at high temperature volatilizees, sol-gal process uses expensive alkoxide, cost is very high, is only suitable for laboratory research.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides a kind of rational in infrastructure, the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide easy to use.
The present invention is achieved through the following technical solutions:
An electrochemical preparation method for solid electrolyte lithium lanthanum titanium oxide is that raw material comprises the following steps with titanium dioxide:
(1) raw material titanium dioxide, binding agent, conductive agent are mixed, tabletted;
(2) with the sheet of compacting in step (1) for positive pole, lithium sheet is that negative pole is assembled into battery, calculates the electricity that embedding lithium needs, electric discharge instrument discharges according to the quality of titanium dioxide and the ratio of lithium titanium;
(3) after discharge off, take out the positive pole of embedding lithium, add that appropriate lanthanum salt mixes, the high temperature anneal obtains lithium lanthanum titanium oxide.
In step (1), titanium dioxide is nano particle, granular size is 25nm, bulky grain adds the difficulty of Lithium-ion embeding, and embedding lithium may be caused uneven, reduces purity, short grained cost is higher, operating difficulties, the titanium dioxide granule of 25nm is commercial materials ripe at present, is the size of combination property optimum.
Binding agent described in step (1) is the one of Kynoar, polytetrafluoroethylene; Conductive agent is acetylene black, the one of SuperP or mixture; Wherein, binding agent is the 5-20% of raw material gross mass, preferably 10%; Conductive agent is the 5-20% of raw material gross mass, preferably 10%.Binding agent ensure that the intensity of compressing tablet, but can affect the conductivity of compressing tablet too much and increase cost, does not have cementation very little, and mass fraction is 5 ~ 20% is optimal proportion.Conductive agent ensure that the conductivity of compressing tablet in discharge process, but can affect the difficulty of film-making too much and increase cost, acts on not obvious very little, and mass fraction is 5 ~ 20% is optimal proportion.
The method of the mixing of step (1) described raw material comprises ball-milling method and polishing.
Step (2) described battery is button cell.
In step (2), discharge capacity is the electricity that the embedding lithium calculated according to the quality of titanium dioxide and the ratio of lithium titanium needs, lithium lanthanum titanium oxide Li 3xla 2/3-xtiO 3middle lithium titanium mol ratio is 3x:1, then the electricity computing formula required for certain mass titanium dioxide embedding corresponding amount lithium is: mAh, wherein m is the grams of titanium dioxide, and M is the molecular weight of titanium dioxide, and the lithium-inserting amount discharging into now titanium dioxide is 3x just.
In step (2), described electric discharge instrument is cell tester or electrochemical workstation, and under the condition meeting range, select the cell tester of lower range, discharging current controls at below 0.1C as far as possible, ensures that lithium ion can be embedded in titanium dioxide equably.
The described lanthanum salt of step (3) is lanthana, lanthanum hydroxide, lanthanum nitrate, lanthanum oxalate, the one of lanthanum acetate or mixture, preferably lanthana.
The mol ratio of the described lanthanum salt of step (3) and titanium dioxide is (2/3-x): 1, wherein, and 0.06≤x≤1/6, lithium lanthanum titanium oxide Li 3xla 2/3-xtiO 3have the compound of multiple different proportion, the mol ratio of lanthanum and titanium is the ratio-dependent according to end product.
Step (3) described 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 DEG C; The temperature of sintering is 900 ~ 1200 DEG C, preferably 1000 DEG C.Pre-burning can ensure the gas of binding agent, conductive agent and other impurity Sum decomposition generation of removing in material.The sintering of higher temperature can ensure abundant reaction, generates the lithium lanthanum titanium oxide of controllable crystal.
The invention has the beneficial effects as follows: the present invention can accurately control Li-La-Ti ratio, solve the problem that in usual solid phase method, lithium salts volatilization at high temperature causes product purity lower, raw material is cheap simultaneously, technique is simple, just can obtain highly purified lithium lanthanum titanium oxide by electrochemistry and high-temperature process two steps.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is Li prepared by the embodiment of the present invention 1 0.33la 0.557tiO 3xRD figure.
Fig. 2 is Li prepared by the embodiment of the present invention 1 0.33la 0.557tiO 3aC impedance figure.
(5) embodiment
Embodiment 1
Take 0.8g titanium dioxide, 0.1gPVDF and 0.1g acetylene black, grind in mortar and fully mix half an hour, get 0.2g mixture and put into mould, suppress 1 minute under 20MPa pressure in flakes.Compressing tablet is done positive pole, selects CR2032 button cell shell, according to the der group packed battery of negative electrode casing, spring leaf, pad, lithium sheet, barrier film, positive pole, anode cover, drip 5 lithium-ion battery electrolytes, prepare button cell with sealing machine sealing.Be put on cell tester by the button cell of preparation, 0.05C constant-current discharge is to the capacity of 17.69mAh.Take out the compressing tablet after embedding lithium, with 0.181g lanthana ground and mixed after drying, 800 DEG C of pre-burnings 5 hours in Muffle furnace, grind latter 1000 DEG C and again sinter and obtain Li in 10 hours 0.33la 0.557tiO 3, after compressing tablet, testing conductivity is 3.8 × 10 -4s/cm.
Embodiment 2
Take 9g titanium dioxide, 0.5gPVDF and 0.5gSuperP, put into 100ml ball grinder, ratio of grinding media to material is 3:1, grinds and fully mixes for 2 hours, get 0.2g mixture and put into mould, suppresses 1 minute in flakes under 20MPa pressure.Compressing tablet is done positive pole, selects CR2032 button cell shell, according to the der group packed battery of negative electrode casing, spring leaf, pad, lithium sheet, barrier film, positive pole, anode cover, drip 5 lithium-ion battery electrolytes, prepare button cell with sealing machine sealing.Be put on cell tester by the button cell of preparation, 0.05C constant-current discharge is to the capacity of 19.9mAh.Take out the compressing tablet after embedding lithium, with 0.2042g lanthana ground and mixed after drying, 550 DEG C of pre-burnings 5 hours in Muffle furnace, grind latter 1200 DEG C and again sinter and obtain Li in 10 hours 0.33la 0.557tiO 3.

Claims (10)

1. an electrochemical preparation method for solid electrolyte lithium lanthanum titanium oxide, is raw material with titanium dioxide, it is characterized in that: comprise the following steps:
(1) raw material titanium dioxide, binding agent, conductive agent are mixed, tabletted;
(2) with the sheet of compacting in step (1) for positive pole, lithium sheet is that negative pole is assembled into battery, calculates the electricity that embedding lithium needs, electric discharge instrument discharges according to the quality of titanium dioxide and the ratio of lithium titanium;
(3) after discharge off, take out the positive pole of embedding lithium, add that appropriate lanthanum salt mixes, the high temperature anneal obtains lithium lanthanum titanium oxide.
2. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, is characterized in that: described in step (1), titanium dioxide is nano particle, and granular size is 25nm.
3. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, is characterized in that: binding agent described in step (1) is the one of Kynoar, polytetrafluoroethylene; Conductive agent is acetylene black, the one of SuperP or mixture; Wherein, binding agent is the 5-20% of raw material gross mass, preferably 10%; Conductive agent is the 5-20% of raw material gross mass, preferably 10%.
4. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, is characterized in that: the method for the mixing of step (1) described raw material comprises ball-milling method and polishing.
5. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, is characterized in that: step (2) described battery is button cell.
6. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterized in that: in step (2), discharge capacity is the electricity that the embedding lithium calculated according to the quality of titanium dioxide and the ratio of lithium titanium needs, lithium lanthanum titanium oxide Li 3xla 2/3-xtiO 3middle lithium titanium mol ratio is 3x:1, then the electricity computing formula required for certain mass titanium dioxide embedding corresponding amount lithium is: mAh, wherein m is the grams of titanium dioxide, and M is the molecular weight of titanium dioxide, and the lithium-inserting amount discharging into now titanium dioxide is 3x just.
7. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, is characterized in that: in step (2), and electric discharge instrument is cell tester or electrochemical workstation, and discharging current controls at below 0.1C.
8. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, it is characterized in that: the described lanthanum salt of step (3) is lanthana, lanthanum hydroxide, lanthanum nitrate, lanthanum oxalate, the one of lanthanum acetate or mixture, preferably lanthana.
9. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, is characterized in that: the mol ratio of the described lanthanum salt of step (3) and titanium dioxide is (2/3-x): 1, wherein, and 0.06≤x≤1/6.
10. the electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide according to claim 1, is characterized in that: step (3) described 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 DEG C; The temperature of sintering is 900 ~ 1200 DEG C, preferably 1000 DEG C.
CN201510620932.0A 2015-09-25 2015-09-25 A kind of electrochemical preparation method of solid electrolyte lithium lanthanum titanium oxide Active CN105206869B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105731549A (en) * 2016-01-25 2016-07-06 山东玉皇新能源科技有限公司 Preparation method and application of high-purity lithium cobalt oxide cathode material
CN109390626A (en) * 2017-08-08 2019-02-26 深圳格林德能源有限公司 A kind of inorganic solid electrolyte synthesis technology and its solid state battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1789483A (en) * 2005-12-29 2006-06-21 复旦大学 Method for preparing LLTO(lithium lanthanum titanate) film by electron beam heat evaporation
CN1970455A (en) * 2006-12-15 2007-05-30 清华大学 Manufacture method of lithium lanthanum titanium oxide
JP2013229132A (en) * 2012-04-24 2013-11-07 Toyota Motor Corp Electrode sintered body and electrode sintered body manufacturing method
CN104051782A (en) * 2013-03-12 2014-09-17 华为技术有限公司 Lithium lanthanum titanate (LLTO) composite solid-state lithium ion electrolyte material, preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1789483A (en) * 2005-12-29 2006-06-21 复旦大学 Method for preparing LLTO(lithium lanthanum titanate) film by electron beam heat evaporation
CN1970455A (en) * 2006-12-15 2007-05-30 清华大学 Manufacture method of lithium lanthanum titanium oxide
JP2013229132A (en) * 2012-04-24 2013-11-07 Toyota Motor Corp Electrode sintered body and electrode sintered body manufacturing method
CN104051782A (en) * 2013-03-12 2014-09-17 华为技术有限公司 Lithium lanthanum titanate (LLTO) composite solid-state lithium ion electrolyte material, preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105731549A (en) * 2016-01-25 2016-07-06 山东玉皇新能源科技有限公司 Preparation method and application of high-purity lithium cobalt oxide cathode material
CN109390626A (en) * 2017-08-08 2019-02-26 深圳格林德能源有限公司 A kind of inorganic solid electrolyte synthesis technology and its solid state battery
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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