CN104701539B - A kind of method that wet chemistry method prepares manganese-lithium phosphate anode material - Google Patents

A kind of method that wet chemistry method prepares manganese-lithium phosphate anode material Download PDF

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CN104701539B
CN104701539B CN201310667415.XA CN201310667415A CN104701539B CN 104701539 B CN104701539 B CN 104701539B CN 201310667415 A CN201310667415 A CN 201310667415A CN 104701539 B CN104701539 B CN 104701539B
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manganese
lithium
lithium phosphate
warming
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CN104701539A (en
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郝德利
叶丽光
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TIANJIN HEWEI TECHNOLOGY CO LTD
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TIANJIN HEWEI TECHNOLOGY CO LTD
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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

A kind of method that wet chemistry method prepares manganese-lithium phosphate anode material, it is the step of preparation method：(1) analytically pure lithium phosphate and analytically pure phosphoric acid Asia manganese according to mol ratio Li：Mn=1.0~1.02：1 ratio mixing is put into mortar, and adding absolute ethyl alcohol to grind 1 ~ 3 hour to mixture turns into powder；(2) ascorbic acid is added, grinding is uniform, adds 4% poly-vinyl alcohol solution, stirs as pulpous state；(3) slurry is heated to 180 DEG C to be kept for 10 hours, then cools to room temperature, reactor pours out all materials, and 105 DEG C of forced air dryings turn into block；(4) block is warming up to 450 DEG C with 5 DEG C/min of speed under high pure nitrogen protection, is incubated 2 hours, then be warming up to 700 DEG C with 5 DEG C/min of speed and be incubated 4 hours, be cooled to room temperature, grind into powder, cross 100 mesh sieves, obtain lithium manganese phosphate material.

Description

A kind of method that wet chemistry method prepares manganese-lithium phosphate anode material
Technical field
The invention belongs to new chemical energy storage field, more particularly to a kind of wet chemistry method prepares manganese-lithium phosphate anode material Method.
Background technology
Lithium manganese phosphate material is a kind of positive electrode of lithium ion battery, have cheap, abundant raw materials, it is nontoxic, Heat endurance is good, it is higher than energy, have extended cycle life, shelf-life the characteristics of long, security performance is prominent and environmentally safe, its Theoretical specific capacity is 170mAh/g, and theoretical work voltage is about 4.1 V, be a kind of most potential new type lithium ion battery just Pole material.But in place of manganese-lithium phosphate anode material still suffers from some shortcomings, as electrical conductivity is low, ionic diffusion coefficient is low, low temperature The shortcomings of poor performance, multiplying power discharging ability, its application aspect is caused to receive many limitations.Domestic and international research institution or enterprise Industry constantly improves the synthetic method of lithium manganese phosphate material, to improve the performance of lithium manganese phosphate material, one of them effective side Method is that incorporation carbon forms composite into lithium manganese phosphate.This method can effectively improve times of lithium manganese phosphate composite Rate, specific capacity, but improvement of this method for cryogenic property is than relatively limited.Hydrothermal synthesis method prepares lithium manganese phosphate material One of advantage is that the material of synthesis is pure, impurity is few, but the solution of existing hydro-thermal method generally use Mn, Li, P salt or alkali Reacted at high temperature under high pressure, incident to be accessory substance while be present in lithium manganese phosphate product, the problem of bringing separation, And accessory substance may pollute the problem of lithium manganese phosphate product.The concentration ratio of simultaneous reactions thing is relatively low, causes the utilization of reactor Efficiency comparison is low, the low yield of unit equipment.The invention discloses the side that a kind of wet chemistry method prepares manganese-lithium phosphate anode material Method, solve the problems, such as that hydro-thermal method is existing, eliminate the generation of accessory substance, improve unit equipment yield, improve production energy Power.
The content of the invention
It is an object of the invention to provide a kind of method that wet chemistry method prepares manganese-lithium phosphate anode material, using lithium phosphate Be raw material with phosphoric acid Asia manganese, by hydro-thermal reaction prepare lithium manganese phosphate material, solve hydro-thermal method preparation accessory substance separation and The problem of unit equipment low yield, maintain the advantages of hydro-thermal method prepares lithium manganese phosphate material.
The present invention realizes that the technical scheme of purpose is：
A kind of method that wet chemistry method prepares manganese-lithium phosphate anode material, it is the step of preparation method：
(1) analytically pure lithium phosphate and analytically pure phosphoric acid Asia manganese crystal according to mol ratio Li：Mn=1.0~1.02：1 Ratio mixing is put into mortar, and the absolute ethyl alcohol for adding mixture quality 10% finishes to grind 1 ~ 3 hour to ethanol volatilization, mixes Compound turns into powder；
(2) ascorbic acid is added according to the ratio of mixture quality 1%, grinding is uniform, adds identical with mixture quality 4% poly-vinyl alcohol solution, stir as pulpous state；
(3) slurry is poured into hydrothermal reaction kettle, is heated to 180 DEG C and is kept for 10 hours, then cool to room temperature, opened anti- Kettle is answered to pour out all materials, carrying out 105 DEG C of forced air dryings turns into block；
(4) block is warming up to 450 DEG C with 5 DEG C/min of speed under high pure nitrogen protection, is incubated 2 hours, then with 5 DEG C/min of speed is warming up to 700 DEG C and is incubated 4 hours, is naturally cooling to room temperature, takes out material, grind into powder, crosses 100 mesh Sieve, obtains lithium manganese phosphate material；
(5) polyvinyl alcohol described in step (2), it is characterized in that：Molecular weight ranges are 5000 ~ 15000.
Embodiment
With reference to embodiment, the present invention is further described, and following embodiments are illustrative, be not it is limited, Protection scope of the present invention can not be limited with following embodiments.
Embodiment 1
(1) 118.1g lithium phosphates（Shanghai China Lithium Industrial Co., Ltd., purity 98%）With 412.1 phosphoric acid Asia manganese crystal（Point Analyse pure, purity 99%）Mixing is put into mortar, adds 62.5g absolute ethyl alcohols and is finished to grind the volatilization of 3 hours ethanol, mixture into For powder；
(2) 6.25g pharmaceutical grade ascorbic acid is added, grinding is uniform, adds 625g 4% polyvinyl alcohol（Molecular weight 6000）Solution, stirred on small-sized dispersion machine as pulpous state；
(3) slurry is poured into hydrothermal reaction kettle, good seal, is heated to 180 DEG C and is kept for 10 hours, then cool to room Temperature, open reactor and pour out all materials, carrying out 105 DEG C of forced air dryings turns into block；
(4) block under high pure nitrogen protection with 5 DEG C/min of speed is warming up to 450 DEG C with pipe type experiment electric furnace, Insulation 2 hours, then be warming up to 700 DEG C with 5 DEG C/min of speed and be incubated 4 hours, room temperature is naturally cooling to, takes out material, grinding Into powder, 100 mesh sieves are crossed, obtain lithium manganese phosphate material.
The lithium manganese phosphate material prepared is tested, using lithium metal as negative pole, the material is under 0.1C discharge-rates, its gram volume For 150mAh/g.
Embodiment 2
(1) 118.1g lithium phosphates（Shanghai China Lithium Industrial Co., Ltd., purity 98%）With 412.1 phosphoric acid Asia manganese crystal（Point Analyse pure, purity 99%）Mixing is put into mortar, adds 62.5g absolute ethyl alcohols and is finished to grind ethanol volatilization in 1.2 hours, mixture As powder；
(2) 6.25g pharmaceutical grade ascorbic acid is added, grinding is uniform, adds 625g 4% polyvinyl alcohol（Molecular weight 15000）Solution, stirred with small-sized scattered pan mixer as pulpous state；
(3) slurry is poured into hydrothermal reaction kettle, good seal, is heated to 180 DEG C and is kept for 10 hours, then cool to room Temperature, open reactor and pour out all materials, carrying out 105 DEG C of forced air dryings turns into block；
(4) block under high pure nitrogen protection with 5 DEG C/min of speed is warming up to 450 with pipe type experiment electric furnace DEG C, 2 hours are incubated, then be warming up to 700 DEG C with 5 DEG C/min of speed and be incubated 4 hours, room temperature is naturally cooling to, takes out material, Grind into powder, 100 mesh sieves are crossed, obtain lithium manganese phosphate material.
The lithium manganese phosphate material prepared is tested, using lithium metal as negative pole, the material is under 0.1C discharge-rates, its gram volume For 152mAh/g.
Embodiment 3
(1) 120.5g lithium phosphates（Shanghai China Lithium Industrial Co., Ltd., purity 98%）With 412.1 phosphoric acid Asia manganese crystal（Point Analyse pure, purity 99%）Mixing is put into mortar, adds 62.5g absolute ethyl alcohols and is finished to grind the volatilization of 3 hours ethanol, mixture into For powder；
(2) 6.25g pharmaceutical grade ascorbic acid is added, grinding is uniform, adds 625g 4% polyvinyl alcohol（Molecular weight 10000）Solution, stir as pulpous state；
(3) slurry is poured into hydrothermal reaction kettle, is heated to 180 DEG C and is kept for 10 hours, then cool to room temperature, opened anti- Kettle is answered to pour out all materials, carrying out 105 DEG C of forced air dryings turns into block；
(4) block under high pure nitrogen protection with 5 DEG C/min of speed is warming up to 450 with pipe type experiment electric furnace DEG C, 2 hours are incubated, then be warming up to 700 DEG C with 5 DEG C/min of speed and be incubated 4 hours, room temperature is naturally cooling to, takes out material, Grind into powder, 100 mesh sieves are crossed, obtain lithium manganese phosphate material.
The lithium manganese phosphate material prepared is tested, using lithium metal as negative pole, the material is under 0.1C discharge-rates, its gram volume For 151mAh/g.

Claims (2)

1. a kind of method that wet chemistry method prepares manganese-lithium phosphate anode material, it is characterized in that：The step of preparation method is：
(1) analytically pure lithium phosphate and analytically pure phosphoric acid Asia manganese crystal according to mol ratio Li：Mn=1.0~1.02：1 ratio Mixing is put into mortar, and the absolute ethyl alcohol for adding mixture quality 10% finishes to grind to volatilize to ethanol for 1 ~ 3 hour, mixture As powder；
(2) ascorbic acid is added according to the ratio of mixture quality 1%, grinding is uniform, adds and mixture quality identical 4% Poly-vinyl alcohol solution, stir as pulpous state；
(3) slurry is poured into hydrothermal reaction kettle, is heated to 180 DEG C and is kept for 10 hours, then cool to room temperature, open reactor All materials are poured out, carrying out 105 DEG C of forced air dryings turns into block；
(4) block is warming up to 450 DEG C with 5 DEG C/min of speed under high pure nitrogen protection, is incubated 2 hours, then with 5 DEG C/ The speed of minute is warming up to 700 DEG C and is incubated 4 hours, is naturally cooling to room temperature, takes out material, grind into powder, crosses 100 mesh sieves, Obtain lithium manganese phosphate material.
2. the method that a kind of wet chemistry method described in claim 1 prepares manganese-lithium phosphate anode material, it is characterized in that described is poly- Vinyl alcohol molecular weight ranges are 5000 ~ 15000.
CN201310667415.XA 2013-12-07 2013-12-07 A kind of method that wet chemistry method prepares manganese-lithium phosphate anode material Active CN104701539B (en)

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CN105070912A (en) * 2015-07-23 2015-11-18 东北大学 Preparation method of spherical lithium ion battery cathode material lithium manganese phosphate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128215A1 (en) * 2011-03-23 2012-09-27 住友大阪セメント株式会社 Positive electrode active material for lithium ion battery and manufacturing method therefor, lithium ion battery electrode, and lithium ion battery
CN103337628A (en) * 2013-06-18 2013-10-02 常州大学 Method for synthesizing positive material nano lithium manganese phosphate of lithium ion battery
CN103413943A (en) * 2013-08-14 2013-11-27 宁波奈克斯特新材料科技有限公司 Lithium manganese phosphate positive electrode material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128215A1 (en) * 2011-03-23 2012-09-27 住友大阪セメント株式会社 Positive electrode active material for lithium ion battery and manufacturing method therefor, lithium ion battery electrode, and lithium ion battery
CN103337628A (en) * 2013-06-18 2013-10-02 常州大学 Method for synthesizing positive material nano lithium manganese phosphate of lithium ion battery
CN103413943A (en) * 2013-08-14 2013-11-27 宁波奈克斯特新材料科技有限公司 Lithium manganese phosphate positive electrode material and preparation method thereof

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