CN105304938A - Electrochemical preparation method of solid electrolyte lithium aluminum titanium phosphate - Google Patents

Electrochemical preparation method of solid electrolyte lithium aluminum titanium phosphate Download PDF

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Publication number
CN105304938A
CN105304938A CN201510630965.3A CN201510630965A CN105304938A CN 105304938 A CN105304938 A CN 105304938A CN 201510630965 A CN201510630965 A CN 201510630965A CN 105304938 A CN105304938 A CN 105304938A
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Prior art keywords
titanium
lithium
solid electrolyte
electrochemical preparation
titanium phosphate
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CN201510630965.3A
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CN105304938B (en
Inventor
陈建伟
赵成龙
王龙
王瑛
张庆朋
李丽
于文倩
王超武
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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
    • 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
    • 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
    • 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 relates to the technical field of lithium ion batteries, in particular to an electrochemical preparation method of solid electrolyte lithium aluminum titanium phosphate. The electrochemical preparation method comprises the following steps of firstly, preparing a mixture of aluminum oxide and titanium dioxide according to the ratio of aluminum to titanium; secondly, embedding the titanium dioxide into lithium ions through an electrochemical method; thirdly, adding phosphor salts according to the ratio of lithium to aluminum to titanium to phosphorus to form a uniform mixture, and annealing to obtain an LATP solid electrolyte. The electrochemical preparation method disclosed by the invention is low-priced in raw materials and is simple in process; high-purity lithium aluminum titanium phosphate can be obtained by an electrochemical step and a high-temperature treatment step; the ratio of the lithium to the aluminum to the titanium to the phosphorus can be accurately controlled, and the problem that the purity of products is lower caused by volatilization of lithium salts at high temperature in a general solid-phase method is solved.

Description

The electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium
(1) technical field
The present invention relates to technical field of lithium ion, particularly a kind of electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium.
(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, titanium phosphate aluminium lithium Li 1+xal xti 2-x(PO 4) 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 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 the electrochemical preparation method of the solid electrolyte titanium phosphate aluminium lithium that a kind of proportional control is accurate, product purity is high, can be mass-produced.
The present invention is achieved through the following technical solutions:
An electrochemical preparation method for solid electrolyte titanium phosphate aluminium lithium, with titanium dioxide and aluminium oxide, binding agent and conductive agent for raw material, comprises the steps:
(1) above-mentioned raw materials is mixed, tabletted;
(2) be positive pole by the sheet of compacting in step (1), 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 microcosmic salt and mix, the high temperature anneal obtains titanium phosphate aluminium lithium.
More excellent technical scheme of the present invention is:
It is the nano particle of 25nm sized by described titanium dioxide; Bulky grain adds the difficulty of Lithium-ion embeding, and embedding lithium may be caused uneven, and reduce purity, short grained cost is higher, operating difficulties, and the titanium dioxide granule of 25nm is commercial materials ripe at present, is the size of combination property optimum.
In step (1), described binding agent is Kynoar or polytetrafluoroethylene, and conductive agent is a kind of in acetylene black and SuperP or both mixtures; 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, wherein preferably 10%.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, wherein preferably 10%.
In step (1), the mixed method of described raw material is ball-milling method or polishing.
In step (2), described battery is button cell, and electric discharge instrument is cell tester or electrochemical workstation; 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.
In step (2), described 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 Li 1+xal xti 2-x(PO 4) 3middle lithium titanium mol ratio is (1+x): (2-x), then the computing formula of the electricity 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 meets the mol ratio of titanium phosphate aluminium lithium just.
In step (3), in microcosmic salt and titanium dioxide, the mol ratio of titanium, phosphorus is (2-x): 3, wherein, and 0 < x≤1, titanium phosphate aluminium lithium Li 1+xal xti 2-x(PO 4) 3have the compound of multiple different proportion, the mol ratio of lithium, aluminium, titanium, phosphorus is the ratio-dependent according to end product; Microcosmic salt is one or more in red phosphorus, white phosphorus, black phosphorus, phosphorus pentoxide, diphosphorus trioxide, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; Wherein some cost of material is more expensive, the easy moisture absorption of some raw material, the ammonium dihydrogen phosphate of preferably low price stable performance.
In 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 700 DEG C, and the temperature of sintering is 700-1100 DEG C, and preferably the temperature of sintering is 900 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 titanium phosphate aluminium lithium of controllable crystal.
Raw material of the present invention is cheap, technique is simple, highly purified titanium phosphate aluminium lithium can be obtained by electrochemistry and high-temperature process two steps, accurately can control lithium aluminium titanium phosphorus ratio, solve the problem that in usual solid phase method, lithium salts volatilization at high temperature causes product purity lower.
(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 1.3al 0.3ti 1.7(PO 4) 3xRD figure.
(5) embodiment
Below by specific embodiments, the present invention is described in further detail, but these embodiments are only to illustrate, do not limit scope of the present invention.
Embodiment 1:
Take 0.719g titanium dioxide, 0.081g aluminium oxide, 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 36.84mAh.Take out the compressing tablet after embedding lithium, with 0.365g ammonium dihydrogen phosphate ground and mixed after drying, 700 DEG C of pre-burnings 10 hours in Muffle furnace, grind latter 900 DEG C and again sinter and obtain Li in 4 hours 1.3al 0.3ti 1.7(PO 4) 3.
Embodiment 2:
Take 8.09g titanium dioxide, 0.91g aluminium oxide, 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 41.45mAh.Take out the compressing tablet after embedding lithium, with 0.41g ammonium dihydrogen phosphate ground and mixed after drying, 550 DEG C of pre-burnings 10 hours in Muffle furnace, grind latter 1100 DEG C and again sinter and obtain Li in 4 hours 1.3al 0.3ti 1.7(PO 4) 3.

Claims (10)

1. an electrochemical preparation method for solid electrolyte titanium phosphate aluminium lithium, with titanium dioxide and aluminium oxide, binding agent and conductive agent for raw material, is characterized by, comprise the steps: that above-mentioned raw materials mixes by (1), tabletted; (2) be positive pole by the sheet of compacting in step (1), 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 microcosmic salt and mix, the high temperature anneal obtains titanium phosphate aluminium lithium.
2. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, is characterized in that: be the nano particle of 25nm sized by described titanium dioxide.
3. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, is characterized in that: in step (1), and the mixed method of described raw material is ball-milling method or polishing; Binding agent is Kynoar or polytetrafluoroethylene, accounts for the 5-20% of raw material gross mass, and conductive agent is a kind of in acetylene black and SuperP or both mixtures, accounts 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 characterized in that: in step (2), described 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, is characterized in that: in step (2), and the computing formula of described 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 discharging into now titanium dioxide meets the mol ratio of titanium phosphate aluminium lithium just.
6. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 1, is characterized in that: in step (3), and in microcosmic salt and titanium dioxide, the mol ratio of titanium, phosphorus is (2-x): 3, wherein, and 0 < x≤1; Microcosmic salt is one or more in red phosphorus, white phosphorus, black 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 characterized in that: in 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, and the temperature of sintering is 700-1100 DEG C.
8. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 4, it is characterized in that: in step (2), electric discharge instrument is cell tester, and discharging current controls at below 0.1C.
9. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 6, it is characterized in that: in step (3), microcosmic salt is ammonium dihydrogen phosphate.
10. the electrochemical preparation method of solid electrolyte titanium phosphate aluminium lithium according to claim 7, is characterized in that: in step (3), and the temperature of described pre-burning is 700 DEG C, and the temperature of sintering is 900 DEG C.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107128891A (en) * 2016-02-29 2017-09-05 铃木株式会社 The manufacture method of solid electrolyte and solid electrolyte
CN108336398A (en) * 2018-03-26 2018-07-27 湘潭大学 Inorganic/organic polymer composite solid electrolyte film of one kind 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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120295167A1 (en) * 2009-10-16 2012-11-22 Sud-Chemie Ag Phase-pure lithium aluminium titanium phosphate and method for its production and its use
CN104221183A (en) * 2011-11-29 2014-12-17 康宁股份有限公司 Reactive sintering of ceramic lithium-ion solid electrolytes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120295167A1 (en) * 2009-10-16 2012-11-22 Sud-Chemie Ag Phase-pure lithium aluminium titanium phosphate and method for its production and its use
CN104221183A (en) * 2011-11-29 2014-12-17 康宁股份有限公司 Reactive sintering of ceramic lithium-ion solid electrolytes

Non-Patent Citations (1)

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Title
HIDEYUKI MORIMOTO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 cathode for lithium cell", 《JOURNAL OF POWER SOURCES》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107128891A (en) * 2016-02-29 2017-09-05 铃木株式会社 The manufacture method of solid electrolyte and solid electrolyte
CN107128891B (en) * 2016-02-29 2019-09-27 铃木株式会社 The manufacturing method of solid electrolyte and solid electrolyte
CN108336398A (en) * 2018-03-26 2018-07-27 湘潭大学 Inorganic/organic polymer composite solid electrolyte film of one kind 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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