CN105336948A - Lithium aluminum titanium phosphate preparation method - Google Patents

Lithium aluminum titanium phosphate preparation method Download PDF

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Publication number
CN105336948A
CN105336948A CN201510633011.8A CN201510633011A CN105336948A CN 105336948 A CN105336948 A CN 105336948A CN 201510633011 A CN201510633011 A CN 201510633011A CN 105336948 A CN105336948 A CN 105336948A
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Prior art keywords
lithium
aluminium
titanium
titanium phosphate
preparation
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CN201510633011.8A
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CN105336948B (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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention belongs to the technical field of lithium-ion batteries, and specifically discloses a lithium aluminum titanium phosphate preparation method. First, titanium dioxide is embedded into an appropriate amount of lithium ions by electrochemical method, according to the ratio of lithium aluminum titanium phosphate, aluminum and phosphor salts are added to form a homogeneous mixture, and the homogeneous mixture is annealed to obtain a LATP (lithium aluminum titanium phosphate) solid electrolyte. The raw materials are cheaper, the process is simple, high purity lithium aluminum titanium phosphate can be obtained by two steps of electrochemical and high temperature treatment, the ratio of lithium aluminum titanium phosphate can be precisely controlled, and the lower product purity problem caused by volatilization of a lithium salt at high temperature in general solid-phase method can be solved.

Description

The preparation method of titanium phosphate aluminium lithium
(1) technical field
The invention belongs to technical field of lithium ion, particularly a kind of preparation method of 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 preparation method of the 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:
A preparation method for titanium phosphate aluminium lithium, take titanium dioxide as raw material, comprises the steps:
(1) titanium dioxide, binding agent and 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 appropriate aluminium salt and microcosmic salt mixes, the high temperature anneal obtains titanium phosphate aluminium lithium.
More excellent technical scheme of the present invention is:
Described titanium dioxide is nano particle, and granular size is 25nm; 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 mixed method is ball-milling method or polishing; 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 (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), aluminium salt is one or more in aluminium oxide, aluminium hydroxide, aluminum nitrate and aluminium chloride, and 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 aluminium oxide of preferably low price stable performance and ammonium dihydrogen phosphate.
In aluminium salt, microcosmic salt and titanium dioxide, the mol ratio of aluminium, titanium, phosphorus is x:(2-x): 3, wherein 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 aluminium, titanium, phosphorus is the ratio-dependent according to end product.
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, preferably 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 0.8g 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 40.99mAh.Take out the compressing tablet after embedding lithium, with 0.018g aluminium oxide and 0.406g 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 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 46.11mAh.Take out the compressing tablet after embedding lithium, with 0.02g aluminium oxide and 0.487g 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. a preparation method for titanium phosphate aluminium lithium, is raw material with titanium dioxide, it is characterized by, and comprises the steps: that titanium dioxide, binding agent and conductive agent mix by (1), 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 appropriate aluminium salt and microcosmic salt mixes, the high temperature anneal obtains titanium phosphate aluminium lithium.
2. the preparation method of titanium phosphate aluminium lithium according to claim 1, it is characterized in that: described titanium dioxide is nano particle, granular size is 25nm.
3. the preparation method of titanium phosphate aluminium lithium according to claim 1, it is characterized in that: in step (1), described mixed method is ball-milling method or polishing; Binding agent is Kynoar or polytetrafluoroethylene, accounts for the 5-20% of mixed material gross mass, and conductive agent is a kind of in acetylene black and SuperP or both mixtures, accounts for the 5-20% of mixed material gross mass.
4. the preparation method of 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. according to the preparation method of the titanium phosphate aluminium lithium described in claim 1, it is characterized in that: in step (2), 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 preparation method of titanium phosphate aluminium lithium according to claim 1, it is characterized in that: in step (3), aluminium salt is one or more in aluminium oxide, aluminium hydroxide, aluminum nitrate and aluminium chloride, and microcosmic salt is one or more in red phosphorus, white phosphorus, black phosphorus, phosphorus pentoxide, diphosphorus trioxide, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; In aluminium salt, microcosmic salt and titanium dioxide, the mol ratio of aluminium, titanium, phosphorus is x:(2-x): 3, wherein 0 < x≤1.
7. the preparation method of titanium phosphate aluminium lithium according to claim 1, is characterized in that: in step (3), and 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 preparation method of 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 preparation method of titanium phosphate aluminium lithium according to claim 6, it is characterized in that: in step (3), aluminium salt is aluminium oxide, and microcosmic salt is ammonium dihydrogen phosphate.
10. the preparation method of titanium phosphate aluminium lithium according to claim 7, it is characterized in that: in step (3), the temperature of described pre-burning is 700 DEG C, the temperature of sintering is 900 DEG C.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112768755A (en) * 2021-01-04 2021-05-07 长沙矿冶研究院有限责任公司 Preparation method of NASION type solid electrolyte aluminum-containing phosphate

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102280658A (en) * 2011-06-30 2011-12-14 哈尔滨工业大学 Method for manufacturing lithium-ion conductivity solid electrolyte
CN102376945A (en) * 2010-08-20 2012-03-14 三星Sdi株式会社 Negative active material, method of preparing same, and rechargeable lithium battery including same
CN102648153A (en) * 2009-10-16 2012-08-22 南方化学股份公司 Phase-pure lithium-aluminium-titanium phosphate and method for the production and use thereof
WO2013146349A1 (en) * 2012-03-30 2013-10-03 戸田工業株式会社 Method for producing lithium ion conductor
CN103825052A (en) * 2014-02-24 2014-05-28 华中科技大学 Preparation method of NASICON-type lithium ion solid electrolyte
US20140162136A1 (en) * 2012-12-12 2014-06-12 Electronics And Telecommunications Research Institute Method of forming lithium-aluminum-titanium phosphate
US20140370396A1 (en) * 2013-06-14 2014-12-18 Electronics And Telecommunications Research Institute Method of preparing lithium phosphate-based solid electrolyte
CN104466238A (en) * 2014-11-28 2015-03-25 深圳华中科技大学研究院 Doped type solid ceramic electrolyte as well as preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102648153A (en) * 2009-10-16 2012-08-22 南方化学股份公司 Phase-pure lithium-aluminium-titanium phosphate and method for the production and use thereof
CN102376945A (en) * 2010-08-20 2012-03-14 三星Sdi株式会社 Negative active material, method of preparing same, and rechargeable lithium battery including same
CN102280658A (en) * 2011-06-30 2011-12-14 哈尔滨工业大学 Method for manufacturing lithium-ion conductivity solid electrolyte
WO2013146349A1 (en) * 2012-03-30 2013-10-03 戸田工業株式会社 Method for producing lithium ion conductor
US20140162136A1 (en) * 2012-12-12 2014-06-12 Electronics And Telecommunications Research Institute Method of forming lithium-aluminum-titanium phosphate
US20140370396A1 (en) * 2013-06-14 2014-12-18 Electronics And Telecommunications Research Institute Method of preparing lithium phosphate-based solid electrolyte
CN103825052A (en) * 2014-02-24 2014-05-28 华中科技大学 Preparation method of NASICON-type lithium ion solid electrolyte
CN104466238A (en) * 2014-11-28 2015-03-25 深圳华中科技大学研究院 Doped type solid ceramic electrolyte as well as preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112768755A (en) * 2021-01-04 2021-05-07 长沙矿冶研究院有限责任公司 Preparation method of NASION type solid electrolyte aluminum-containing phosphate

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