CN102593451A - Lithium manganese phosphate nanofiber as anode material of lithium ion battery and preparation method of lithium manganese phosphate nanofiber - Google Patents
Lithium manganese phosphate nanofiber as anode material of lithium ion battery and preparation method of lithium manganese phosphate nanofiber Download PDFInfo
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Abstract
The invention relates to a lithium manganese phosphate nanofiber as an anode material of a lithium ion battery and a preparation method of the lithium manganese phosphate nanofiber. The preparation method includes the following steps: mixing and ball milling a lithium source, a manganese source, a phosphorus source and a carbon source to obtain a nanofiber-shaped lithium manganese phosphate precursor; thermally treating the lithium manganese phosphate precursor in the protective atmosphere; and crushing, ball milling and sieving the thermally-treated product to obtain the lithium manganese phosphate nanofiber as the anode material of the lithium ion battery. The preparation method is simple in process and is low in cost; and the lithium manganese phosphate nanofiber as the anode material of the lithium ion battery, which is high in purity and favorable in crystallizing performance, can be obtained.
Description
Technical field
The present invention relates to the lithium ion battery material technical field, particularly, the present invention relates to a kind of lithium ion battery anode material manganese lithium phosphate nanofiber and preparation method thereof.
Background technology
In recent years; Obtained extensive use as the lithium ion battery of novel green power supply in high capacity cell fields such as portable type electronic product and power, energy storage; Wherein, anode material for lithium-ion batteries then is one of key technology that has constituted present lithium ion battery update.
The olivine structural series of phosphate material that uses as anode material for lithium-ion batteries mainly comprises LiFePO
4, LiMnPO
4, LiCoPO
4And LiNiPO
4Four kinds of materials, its embedding lithium current potential is respectively 3.45V, 4.1V, 4.8V and 5.1V.LiCoPO
4The prices of raw and semifnished materials higher, and the toxicity of cobalt is big, and LiNiPO
4Then owing to the electrolyte that does not have at present to match, therefore, people are less to the research of the two at present.LiFePO
4Because of having advantages of higher stability and fail safe, environmental protection and advantage such as cheap has become the research focus of anode material for lithium-ion batteries in recent years, still, LiFePO
4Also there is certain shortcoming: the one, voltage platform lower (3.45V), thus cause its volume and mass energy density not high; It two is that theoretical capacity is not high, and room-temperature conductivity is low; Though it three is that its prices of raw and semifnished materials are low, harsh synthesis condition causes the finished product price very high.
By contrast, anode material for lithium-ion batteries LiMnPO
4Not only the cost of raw material is cheap, and is also not high to the synthesis condition requirement, even can in air atmosphere, synthesize, and its operating voltage is up to 4.1V, with LiFePO
4Compare and have higher volume and mass energy density, therefore have more application potential.At present, reported about LiMnPO
4The preparation method mainly contain solid phase method, sol-gel process, hydro thermal method etc.; As; CN 101853936A discloses " preparation method of lithium ion battery anode material manganese lithium phosphate ", and its principal character is 2～5h to be calcined earlier in lithium source, manganese source and phosphorus source make presoma in 250～350 ℃ air atmosphere, then with presoma grinding, compressing tablet; And continued heats 15～25h acquisition lithium manganese phosphate in 500～900 ℃ air atmosphere; This method adopts 2 footworks to prepare target product, and the centre also needs complicated technologies such as compressing tablet, at high temperature calcines at last to obtain the solid-phase sintering particle in several hours.CN 101944615A discloses " a kind of lithium ion battery is with lithium manganese phosphate positive electrode and preparation method thereof "; Its principal character is under nitrogen or argon gas atmosphere protection, lithium source, manganese source, phosphorus source and carbon source to be mixed several hours; Then this mixture is processed the module that density is 0.5～3.0 gram/cubic centimetre under 3～12MPa; At last this module was obtained lithium manganese phosphate in 10～12 hours at 600～850 ℃ of constant temperature calcinings, this method need be processed module with mixture under the pressure of 3～12MPa, then in high-temperature roasting; And in the whole process of batch mixing and roasting, all adopting inert atmosphere protection, complex process and cost are higher.(Precursor-based synthesis and electrochemical performance of LiMnPO such as Natalia N.Bramnik
4, Journal of Alloys and Compounds 464 (2008) 259-264) and adopt sol-gel process to prepare LiMnPO
4, its principal character is to have prepared pattern to be about group's bunch body of 50m for the average-size of being made up of less than numerous granules of 300nm the individual particle size, this method process route complicacy is not suitable for suitability for industrialized production.(Effect of copper doping on LiMnPO such as Jiangfeng Ni
4Prepared via hydrothermal route, Journal of Power Sources 196 (2011) 6498-6501) adopt Hydrothermal Preparation most of particle sizes be the Cu Li doped MnPO of 100nm
4Its principal character is in presoma preparation and water-heat process, all to need argon shield; Hydrothermal product need be used deionized water and ethanol repeatedly to wash and be dry; Again it is obtained target product at 600 ℃ of calcining 1h at last, though this method has obtained the Cu Li doped MnPO that most of particle sizes are 100nm
4But complicated process of preparation, especially the repeated multiple times washing to hydrothermal product more are not suitable for industrialization promotion.
In sum, adopt existing method to prepare LiMnPO
4The time all have complicated process of preparation, problem that cost is high mostly, the particle size of product further influences its final chemical property than senior general simultaneously.Therefore; The present invention provides a kind of lithium ion battery anode material manganese lithium phosphate nanofiber and preparation method thereof; Adopt simple preparation technology, through selecting suitable raw material, finally preparing diameter in conjunction with the ball-milling technology of optimizing is less than 100nm and the good LiMnPO of crystallinity
4Nanofiber, the present invention is for improving the LiMnPO that electrical property provides more simply effectively, has been more suitable for industrial applications through reducing particle diameter
4The preparation method.
Summary of the invention
In order to solve present LiMnPO
4Mostly all there are complicated process of preparation, problem that cost is high in the preparation process; The particle size of product will further influence the outstanding technical problem of its final chemical property more greatly simultaneously; One of the object of the invention provides and a kind ofly adopts simple solid phase preparation technology to prepare the method for lithium ion battery anode material manganese lithium phosphate nanofiber; This method not only technology is simple; Can prepare high-purity phosphoric acid manganese lithium nanofiber, and the preparation cost of lithium manganese phosphate is reduced greatly, be more suitable for suitability for industrialized production.
The preparation method of said lithium ion battery anode material manganese lithium phosphate nanofiber may further comprise the steps:
(1) lithium source, manganese source, phosphorus source, carbon source are added ball mill and carry out wet-milling;
(2) product of step (1) is changed in the ultra-fine mill continue ball milling, obtain nanometer fibrous lithium manganese phosphate presoma;
(3) the nanometer fibrous lithium manganese phosphate presoma that step (2) is obtained is heat-treated in protective atmosphere, obtains the heat treatment product;
(4) the heat treatment product that step (3) is obtained obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
Preferably, the preparation method of said lithium ion battery anode material manganese lithium phosphate nanofiber may further comprise the steps:
(1 ') adds ball mill with lithium source, manganese source, phosphorus source and carries out wet-milling, adds carbon source then and continues wet-milling;
(2) product of step (1 ') is changed in the ultra-fine mill continue ball milling, obtain nanometer fibrous lithium manganese phosphate presoma;
(3) the nanometer fibrous lithium manganese phosphate presoma that step (2) is obtained is heat-treated in protective atmosphere, obtains the heat treatment product;
(4) the heat treatment product that step (3) is obtained obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
Preferably; The mol ratio of lithium, manganese, phosphorus is (0.9～1.1) in step (1) and/or (1 ') said lithium source, manganese source, the phosphorus source: (0.9～1.1): (0.9～1.1); For example: 0.91: 1.09: 1.09,0.91: 1: 1,1.09: 0.91: 0.91,0.95: 1: 0.91,1.09: 0.91: 1.09 etc.; Further be preferably (0.95～1.1): (0.95～1.05): (0.95～1.05) is preferably (1～1.05): 1: 1 especially.
Preferably; Step (1) and/or (1 ') said carbon source are 0.01～65% of lithium manganese phosphate product quality; For example: 0.02%, 0.03%, 0.09%, 0.5%, 1%, 5%, 10%, 20%, 40%, 50%, 60%, 64%, 64.5%, 64.9% etc.; Further be preferably 0.05～60%, be preferably 0.1～55% especially.
Preferably; Lithium dihydrogen phosphate is contained in step (1) and/or (1 ') said lithium source; Further preferred said lithium source is a lithium dihydrogen phosphate; Or a kind or at least 2 kinds the combination and the mixture of lithium dihydrogen phosphate in the lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium oxalate, lithium sulfate; Said combination typical case but nonrestrictive example have: the combination of lithium carbonate, lithium acetate, the combination of lithium acetate, lithium formate, lithium citrate, the combination of lithium hydroxide, tert-butyl alcohol lithium, lithium oxalate; The combination of lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, phosphoric acid hydrogen two lithiums; The combination of lithium phosphate, phosphoric acid hydrogen two lithiums, lithium oxalate, lithium sulfate, the combination of lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithiums, the combination of lithium bromide, lithium hydroxide, tert-butyl alcohol lithium etc.; Be preferably lithium dihydrogen phosphate especially, or a kind or at least 2 kinds the combination and the mixture of lithium dihydrogen phosphate in the lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate.
Preferably; Manganese carbonate is contained in step (1) and/or (1 ') said manganese source; Further preferred said manganese source is a manganese carbonate; Or a kind or at least 2 kinds the combination and the mixture of manganese carbonate in the manganese phosphate, manganese oxalate, manganous hydroxide, manganese nitrate, manganese acetate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide, said combination typical case but nonrestrictive example have: the combination of manganese phosphate, manganese oxalate, the combination of manganous hydroxide, manganese nitrate; The combination of manganese oxalate, manganous hydroxide, manganese nitrate; The combination of manganous hydroxide, manganese nitrate, manganese dioxide, the combination of manganous hydroxide, manganese nitrate, manganese acetate, mangano-manganic oxide, the combination of manganese phosphate, manganese oxalate, manganous hydroxide, manganese sesquioxide managnic oxide, manganese dioxide etc.; Preferred especially said manganese source is a manganese carbonate, or a kind or at least 2 kinds the combination and the mixture of manganese carbonate in the manganese phosphate, manganese oxalate, manganous hydroxide, manganese nitrate, manganese acetate.
Preferably; Step (1) and/or (1 ') said phosphorus source are a kind or at least 2 kinds combination in lithium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, phosphoric acid, phosphorous acid, pyrophosphoric acid, the diammonium hydrogen phosphate; Said combination typical case but nonrestrictive example have: the combination of lithium dihydrogen phosphate, ammonium phosphate; The combination of ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate; The combination of ammonium dihydrogen phosphate, phosphorus pentoxide, phosphoric acid; The combination of phosphorus pentoxide, phosphoric acid, phosphorous acid, pyrophosphoric acid; The combinations of lithium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate etc. further are preferably a kind or at least 2 kinds combination in lithium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, phosphoric acid, the diammonium hydrogen phosphate, are preferably a kind or at least 2 kinds combination in lithium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, the phosphorus pentoxide especially.
Preferably; Step (1) and/or (1 ') said carbon source are a kind or at least 2 kinds combination in carbohydrate, polyvinyl alcohol, polyethylene glycol, coke, coal tar pitch, carbon black, acetylene black, epoxy resin, the citric acid; Further be preferably a kind or at least 2 kinds combination in cellulose, polyvinyl alcohol, polyethylene glycol, soluble starch, coke, dextrin, coal tar pitch, carbon black, acetylene black, epoxy resin, sucrose, monocrystalline/polycrystalline rock sugar, glucose, fructose, lactose, the ascorbic acid; Said combination typical case but non-limiting instance have: the combination of cellulose, polyvinyl alcohol; The combination of polyethylene glycol, soluble starch; The combination of coke, dextrin, coal tar pitch; The combination of carbon black, acetylene black, lactose; The combination of epoxy resin, sucrose, monocrystalline/polycrystalline rock sugar, ascorbic acid; The combination of glucose, fructose, lactose, ascorbic acid, the combination of coke, dextrin, coal tar pitch, carbon black, acetylene black, epoxy resin etc. are preferably a kind or at least 2 kinds combination in cellulose, polyvinyl alcohol, polyethylene glycol, soluble starch, coke, dextrin, coal tar pitch, carbon black, acetylene black, epoxy resin, sucrose, monocrystalline/polycrystalline rock sugar, glucose, the fructose especially.
Preferably; The used solvent of wet-milling contains deionized water described in step (1) and/or the step (1 '); Further preferred used solvent is a deionized water; 1 kind or at least 2 kinds the combination and the mixture of deionized water in perhaps water-soluble alcohols, ketone, the alkane are preferably deionized water especially, perhaps a kind in absolute ethyl alcohol, polyvinyl alcohol, ethylene glycol, n-butanol, isobutanol, acetone, the cyclohexane or at least 2 kinds the combination and the mixture of deionized water; Said combination is typical but nonrestrictive example has the combination of water-ethanol, polyvinyl alcohol; The combination of ethylene glycol, n-butanol, isobutanol, the combination of isobutanol, acetone, cyclohexane, the combination of n-butanol, isobutanol, acetone, cyclohexane etc.
Preferably; The wet-milling time described in the step (1) is more than 2 hours; For example 2.1 hours, 2.2 hours, 2.5 hours, 3 hours, 5 hours, 8 hours, 11 hours, 15 hours, 18 hours, 24 hours etc.; Further be preferably more than 4 hours, more preferably more than 6 hours, be preferably especially more than 10 hours.
Preferably; The said wet-milling time is more than 1 hour before to add carbon source in the step (1 '); For example: 1.1 hours, 1.2 hours, 1.5 hours, 2 hours, 5 hours, 8 hours, 11 hours, 15 hours, 20 hours, 24 hours etc.; Further be preferably 1.5～20 hours, be preferably 2～12 hours especially.
Preferably; The said wet-milling time is more than 1 hour after adding carbon source in the step (1 '); For example: 1.1 hours, 1.2 hours, 1.5 hours, 2 hours, 5 hours, 8 hours, 9 hours, 9.9 hours, 20 hours, 24 hours etc.; Further be preferably 1.5～10 hours, be preferably 2～6 hours especially.
Preferably, wet-milling described in the step (1) is wet-milling while stirring, particularly preferably in ball milling while stirring in the agitating ball mill.
Preferably, add in the step (1 ') before the carbon source and/or said afterwards wet-milling is wet-milling while stirring, particularly preferably in ball milling while stirring in the agitating ball mill.
Preferably; The ball milling time described in the step (2) is more than 1 hour; For example: 1.1 hours, 1.2 hours, 1.5 hours, 2 hours, 5 hours, 8 hours, 11 hours, 15 hours, 20 hours, 24 hours etc., further be preferably 1.5～20 hours, be preferably 2～16 hours especially.
Preferably, ball milling described in the step (2) carries out drying after finishing, and obtains nanometer fibrous lithium manganese phosphate presoma, especially preferably after the drying equipment intensive drying, obtains nanometer fibrous lithium manganese phosphate presoma; Preferably, said drying equipment is a kind or at least 2 kinds combination in turning circle cartridge type drying machine, pneumatic drier, vacuum drying chamber, the air dry oven.
Preferably, protective atmosphere is inert gas or weakly reducing atmosphere described in the step (3); Preferred especially, said inert gas or weakly reducing atmosphere be argon gas, nitrogen, added a kind or at least 2 kinds combination in the gaseous mixture of nitrogen and/or argon gas of hydrogen; Preferably, the addition of said hydrogen is mark 0.1～10% by volume, further is preferably 0.5～8%, is preferably 1～5% especially; Preferably, said nitrogen and/or argon gas are high-purity gas, and said high-purity finger purity is equal to or higher than 99.999%.
Preferably; The heat treatment programming rate is below 40 ℃/minute described in the step (3); For example:; 0.1 ℃ of/minute, 0.5 ℃/minute, 0.9 ℃/minute, 1.1 ℃/minute, 2 ℃/minute, 3 ℃/minute, 5 ℃/minute, 10 ℃/minute, 15 ℃/minute, 25 ℃/minute, 29 ℃/minute, 39 ℃/minute, 39.5 ℃/minute etc., further be preferably 1～30 ℃/minute, be preferably 2～20 ℃/minute especially.
Preferably, heat treatment described in the step (3) is carried out with 100～550 ℃ and 550～1100 ℃ of two temperature sections successively; Preferably, first temperature section is 150～520 ℃, is preferably 200～500 ℃ especially; Preferably, second temperature section is 580～1000 ℃, is preferably 600～900 ℃ especially; Preferably, said two temperature sections all are temperature constant state, promptly after first temperature section carries out constant temperature calcining, are warming up to second temperature section and carry out constant temperature calcining; Preferably; Said first temperature section heat treatment time is more than 1 hour; For example: 1.1 hours, 1.2 hours, 1.5 hours, 2 hours, 5 hours, 8 hours, 11 hours, 15 hours, 20 hours, 24 hours etc., further be preferably more than 2 hours, be preferably 3～10 hours especially; Preferably; Said second temperature section heat treatment time is more than 2 hours; For example: 2.1 hours, 2.2 hours, 2.5 hours, 3 hours, 5 hours, 8 hours, 20 hours, 25 hours, 30 hours, 35 hours etc., further be preferably more than 4 hours, be preferably 6～24 hours especially.
One of the object of the invention also is to provide a kind of lithium ion battery anode material manganese lithium phosphate nanofiber, it is characterized in that, said nanofiber is prepared by the method for the invention, and its diameter is less than 100nm.
Outstanding advantage of the present invention and good effect are following:
(1) the present invention utilizes ball grinding technique to adopt simple process to prepare lithium manganese phosphate nanofiber presoma at normal temperatures and pressures; And then through being that final objective product lithium manganese phosphate nanofiber is prepared in 550～1100 ℃ of heat treatments in maximum temperature; Reduced production cost and energy consumption, solved present lithium manganese phosphate and prepared complex process in the process, problem that cost is high;
(2) the prepared lithium manganese phosphate nanofiber of the present invention; Its diameter is less than 100nm; And purity is high, and crystallinity is good, and this is for providing more simply effectively, be more suitable for the LiMnPO of industrial applications through the chemical property that reduces particle diameter raising anode material for lithium-ion batteries
4The preparation method;
(3) method for preparing the lithium ion battery anode material manganese lithium phosphate nanofiber provided by the invention; Not only simple to operate; And controllability is strong, environmentally safe, and rational heat treatment technology has been guaranteed the good crystallinity and the uniformity of prepared lithium manganese phosphate nanofiber;
(4) lithium manganese phosphate nanofiber provided by the invention has great actual application value, has boundless industrial applications prospect as anode material for lithium-ion batteries.
Description of drawings
Fig. 1 be among the embodiment 1 after the ball milling drying nanometer fibrous lithium manganese phosphate presoma amplify 100,000 times electromicroscopic photograph.
Fig. 2 be among the embodiment 1 after the ball milling drying nanometer fibrous lithium manganese phosphate presoma amplify 60,000 times electromicroscopic photograph.
Fig. 3 is the XRD spectra of 8 hours afterproduct lithium manganese phosphates of 710 ℃ of roastings nanofiber among the embodiment 2.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
A certain amount of lithium dihydrogen phosphate of weighing and manganese carbonate in proportion; The mol ratio that makes lithium, manganese, phosphorus is 1: 1: 1; It is added in deionized water, ball milling 2 hours while stirring in agitating ball mill, then; Adding the quality percentage composition is the polyvinyl alcohol of lithium manganese phosphate product 0.1%; Continue stirring ball-milling and change in the ultra-fine mill them over to ball milling 16 hours after 2 hours again, the mixture that will pass through behind the ultra-fine abrading-ball mill obtains nanometer fibrous lithium manganese phosphate presoma after the intensive drying in pneumatic drier, and its stereoscan photograph under different amplification is as depicted in figs. 1 and 2.At last; Dried lithium manganese phosphate presoma is heat-treated with 5 ℃/minute programming rate in argon gas atmosphere; In the heat treatment process 200 ℃ of constant temperature calcinings 3 hours; Then 600 ℃ of constant temperature calcinings 24 hours, the heat treatment product obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
Embodiment 2
A certain amount of lithium dihydrogen phosphate of weighing, lithium carbonate and manganese carbonate in proportion; The mol ratio that makes lithium, manganese, phosphorus is 1.05: 1: 1, it is added in the mixed liquor of deionized water and absolute ethyl alcohol ball milling 12 hours while stirring in agitating ball mill; Then; Adding the quality percentage composition is the mixture of polyvinyl alcohol, cellulose and the carbon black of lithium manganese phosphate product 10%, continues stirring ball-milling and changes in the ultra-fine mill them over to ball milling 2 hours after 6 hours again, and the mixture that will pass through behind the ultra-fine abrading-ball mill obtains nanometer fibrous lithium manganese phosphate presoma after the intensive drying in blast drier; At last; Dried lithium manganese phosphate presoma is heat-treated with 10 ℃/minute programming rate in nitrogen atmosphere, in the heat treatment process 350 ℃ of constant temperature calcinings 10 hours, then 710 ℃ of constant temperature calcinings 8 hours; The heat treatment product obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving; The result is as shown in Figure 3 for its XRD analysis, can be known by the XRD interpretation of result, and product is the lithium manganese phosphate of pure phase.
Embodiment 3
A certain amount of lithium dihydrogen phosphate of weighing, ammonium dihydrogen phosphate, lithium carbonate, lithium chloride, manganese carbonate and manganese acetate in proportion; The mol ratio that makes lithium, manganese, phosphorus is 1.03: 1: 1; It is added in the mixed liquor of deionized water, absolute ethyl alcohol and acetone; Ball milling 4 hours while stirring in agitating ball mill; Then, adding the quality percentage composition is the polyethylene glycol of lithium manganese phosphate product 5% and the mixture of monocrystal rock sugar, and the continuation stirring ball-milling changed in the ultra-fine mill them over to ball milling 6 hours after 3 hours again; The mixture that will pass through after ultra-fine abrading-ball grinds obtains nanometer fibrous lithium manganese phosphate presoma after the intensive drying in pneumatic drier; At last, dried lithium manganese phosphate presoma is heat-treated with 2 ℃/minute programming rate in volume fraction is the mist of 1% hydrogen and 99% high pure nitrogen, in the heat treatment process 500 ℃ of constant temperature calcinings 6 hours; Then 650 ℃ of constant temperature calcinings 20 hours, the heat treatment product obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
Embodiment 4
A certain amount of lithium dihydrogen phosphate of weighing, phosphorus pentoxide, lithium hydroxide, lithium benzoate, manganese carbonate and manganese oxalate in proportion; The mol ratio that makes lithium, manganese, phosphorus is 1.02: 1: 1; It is added in the mixed liquor of deionized water, isobutanol and cyclohexane, ball milling 6 hours while stirring in agitating ball mill, then; Adding the quality percentage composition is the mixture of coke, dextrin and the epoxy resin of lithium manganese phosphate product 20%; Continue stirring ball-milling and change in the ultra-fine mill them over to ball milling 8 hours after 4 hours again, the mixture that will pass through behind the ultra-fine abrading-ball mill obtains nanometer fibrous lithium manganese phosphate presoma after the intensive drying in vacuum drying chamber, last; Dried lithium manganese phosphate presoma is heat-treated with 10 ℃/minute programming rate in argon gas atmosphere; 450 ℃ of constant temperature calcinings 5 hours, then 790 ℃ of constant temperature calcinings 12 hours, the heat treatment product obtained the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving in the heat treatment process.
Embodiment 5
A certain amount of lithium dihydrogen phosphate of weighing, ammonium phosphate, lithium carbonate, manganese carbonate and manganese nitrate in proportion; The mol ratio that makes lithium, manganese, phosphorus is 1.02: 1: 1; It is added in the mixed liquor of deionized water, absolute ethyl alcohol and n-butanol; Ball milling 8 hours while stirring in agitating ball mill; Adding the quality percentage composition is the mixture of polyethylene glycol, coal tar pitch and the fructose of lithium manganese phosphate product 30%; Continue stirring ball-milling and change in the ultra-fine mill them over to ball milling 12 hours after 5 hours again, the mixture that will pass through behind the ultra-fine abrading-ball mill obtains nanometer fibrous lithium manganese phosphate presoma after the intensive drying in air dry oven, last; Dried lithium manganese phosphate presoma, volume fraction is heat-treated with 15 ℃/minute programming rate in being the mist of 3% hydrogen and 97% high-purity argon gas; 400 ℃ of constant temperature calcinings 8 hours, then 850 ℃ of constant temperature calcinings 10 hours, the heat treatment product obtained the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving in the heat treatment process.
Embodiment 6
A certain amount of lithium dihydrogen phosphate of weighing, lithium carbonate, lithium hydroxide, manganese carbonate and manganous hydroxide in proportion; The mol ratio that makes lithium, manganese, phosphorus is 1.04: 1: 1; It is added in the mixed liquor of deionized water, absolute ethyl alcohol and polyvinyl alcohol; Ball milling 10 hours while stirring in agitating ball mill; Then, adding the quality percentage composition is the mixture of polyethylene glycol, epoxy resin, sucrose and the acetylene black of lithium manganese phosphate product 40%, continues stirring ball-milling and changes in the ultra-fine mill them over to ball milling 4 hours after 3.5 hours again; The mixture that will pass through after ultra-fine abrading-ball grinds obtains nanometer fibrous lithium manganese phosphate presoma after the intensive drying in turning circle cartridge type drying machine; At last, dried lithium manganese phosphate presoma is heat-treated with 12 ℃/minute programming rate in volume fraction is the mist of 5% hydrogen and 95% high pure nitrogen, in the heat treatment process 550 ℃ of constant temperature calcinings 4 hours; Then 900 ℃ of constant temperature calcinings 6 hours, the heat treatment product obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
In proportion a certain amount of lithium dihydrogen phosphate of weighing, lithium oxalate, phosphoric acid hydrogen two lithiums, manganese carbonate, manganese oxalate,, manganous hydroxide and phosphoric acid; The mol ratio that makes lithium, manganese, phosphorus is 1.1: 0.9: 0.9; It is added in the mixed liquor of deionized water and n-butanol; Ball milling 20 hours while stirring in agitating ball mill; Then, adding the quality percentage composition is the mixture of glucose, fructose, lactose and the ascorbic acid of lithium manganese phosphate product 0.01%, continues stirring ball-milling and changes in the ultra-fine mill them over to ball milling 20 hours after 1 hour again; The mixture that will pass through after ultra-fine abrading-ball grinds obtains nanometer fibrous lithium manganese phosphate presoma after the intensive drying in turning circle cartridge type drying machine; At last, dried lithium manganese phosphate presoma is heat-treated with 40 ℃/minute programming rate in volume fraction is respectively the mist of 0.1% hydrogen and 99.9% high pure nitrogen, in the heat treatment process 100 ℃ of constant temperature calcinings 15 hours; Then 1100 ℃ of constant temperature calcinings 2 hours, the heat treatment product obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
Embodiment 8
A certain amount of lithium dihydrogen phosphate of weighing, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, manganese carbonate, mangano-manganic oxide, phosphoric acid and diammonium hydrogen phosphate in proportion; The mol ratio that makes lithium, manganese, phosphorus is 0.9: 1: 1.1; It is added in the mixed liquor of deionized water, n-butanol, isobutanol; Ball milling 1 hour while stirring in agitating ball mill; Then, add the mixture of acetylene black that the quality percentage composition is a lithium manganese phosphate product 65%, epoxy resin, sucrose, monocrystalline/polycrystalline rock sugar, continue stirring ball-milling and change in the ultra-fine mill again it over to ball milling 1 hour after 15 hours; The mixture that will pass through after ultra-fine abrading-ball grinds obtains nanometer fibrous lithium manganese phosphate presoma after the intensive drying in turning circle cartridge type drying machine; At last, dried lithium manganese phosphate presoma is heat-treated with 1 ℃/minute programming rate in volume fraction is the mist of 10% hydrogen and 90% high-purity argon gas, in the heat treatment process 500 ℃ of constant temperature calcinings 1 hour; Then 600 ℃ of constant temperature calcinings 24 hours, the heat treatment product obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the preparation method of a lithium ion battery anode material manganese lithium phosphate nanofiber may further comprise the steps:
(1) lithium source, manganese source, phosphorus source, carbon source are added ball mill and carry out wet-milling;
(2) product of step (1) is changed in the ultra-fine mill continue ball milling, obtain nanometer fibrous lithium manganese phosphate presoma;
(3) the nanometer fibrous lithium manganese phosphate presoma that step (2) is obtained is heat-treated in protective atmosphere, obtains the heat treatment product;
(4) the heat treatment product that step (3) is obtained obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
2. method according to claim 1 is characterized in that, said method comprising the steps of:
(1 ') adds ball mill with lithium source, manganese source, phosphorus source and carries out wet-milling, adds carbon source then and continues wet-milling;
(2) product of step (1 ') is changed in the ultra-fine mill continue ball milling, obtain nanometer fibrous lithium manganese phosphate presoma;
(3) the nanometer fibrous lithium manganese phosphate presoma that step (2) is obtained is heat-treated in protective atmosphere, obtains the heat treatment product;
(4) the heat treatment product that step (3) is obtained obtains the lithium ion battery anode material manganese lithium phosphate nanofiber through pulverizing, ball milling, after sieving.
3. according to claim 1 or claim 2 method; It is characterized in that; The mol ratio of lithium, manganese, phosphorus is preferably (0.9～1.1) in step (1) and/or (1 ') said lithium source, manganese source, the phosphorus source: (0.9～1.1): (0.9～1.1); Further be preferably (0.95～1.1): (0.95～1.05): (0.95～1.05) is preferably (1～1.05): 1: 1 especially;
Preferably, step (1) and/or (1 ') said carbon source are 0.01～65% of lithium manganese phosphate product quality, further are preferably 0.05～60%, are preferably 0.1～55% especially.
4. like each described method of claim 1-3; It is characterized in that; Lithium dihydrogen phosphate is preferably contained in step (1) and/or (1 ') said lithium source; Further preferred said lithium source is a lithium dihydrogen phosphate; Or a kind or at least 2 kinds the combination and the mixture of lithium dihydrogen phosphate in the lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium oxalate, lithium sulfate; Be preferably lithium dihydrogen phosphate especially, or a kind or at least 2 kinds the combination and the mixture of lithium dihydrogen phosphate in the lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate;
Preferably; Manganese carbonate is contained in step (1) and/or (1 ') said manganese source; Further preferred said manganese source is a manganese carbonate; Or a kind or at least 2 kinds the combination and the mixture of manganese carbonate in the manganese phosphate, manganese oxalate, manganous hydroxide, manganese nitrate, manganese acetate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide, preferred especially said manganese source is a manganese carbonate, or a kind or at least 2 kinds the combination and the mixture of manganese carbonate in the manganese phosphate, manganese oxalate, manganous hydroxide, manganese nitrate, manganese acetate.
5. like each described method of claim 1-4; It is characterized in that; Step (1) and/or (1 ') said phosphorus source are preferably a kind or at least 2 kinds combination in lithium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, phosphoric acid, phosphorous acid, pyrophosphoric acid, the diammonium hydrogen phosphate; Further be preferably a kind or at least 2 kinds combination in lithium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, phosphoric acid, the diammonium hydrogen phosphate, be preferably a kind or at least 2 kinds combination in lithium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, the phosphorus pentoxide especially;
Preferably; Step (1) and/or (1 ') said carbon source are a kind or at least 2 kinds combination in carbohydrate, polyvinyl alcohol, polyethylene glycol, coke, coal tar pitch, carbon black, acetylene black, epoxy resin, the citric acid; Further be preferably a kind or at least 2 kinds combination in cellulose, polyvinyl alcohol, polyethylene glycol, soluble starch, coke, dextrin, coal tar pitch, carbon black, acetylene black, epoxy resin, sucrose, monocrystalline/polycrystalline rock sugar, glucose, fructose, lactose, the ascorbic acid, be preferably a kind or at least 2 kinds combination in cellulose, polyvinyl alcohol, polyethylene glycol, soluble starch, coke, dextrin, coal tar pitch, carbon black, acetylene black, epoxy resin, sucrose, monocrystalline/polycrystalline rock sugar, glucose, the fructose especially.
6. like each described method of claim 1-5; It is characterized in that; The used solvent of wet-milling preferably contains deionized water described in step (1) and/or the step (1 '); Further preferred used solvent is a deionized water; 1 kind or at least 2 kinds the combination and the mixture of deionized water in perhaps water-soluble alcohols, ketone, the alkane are preferably deionized water especially, perhaps a kind in absolute ethyl alcohol, polyvinyl alcohol, ethylene glycol, n-butanol, isobutanol, acetone, the cyclohexane or at least 2 kinds the combination and the mixture of deionized water;
Preferably, the wet-milling time described in the step (1) is more than 2 hours, further is preferably more than 4 hours, more preferably more than 6 hours, is preferably especially more than 10 hours.
7. like each described method of claim 1-6, it is characterized in that the said wet-milling time was preferably more than 1 hour before the middle adding of step (1 ') carbon source, further was preferably 1.5～20 hours, was preferably 2～12 hours especially;
Preferably, the said wet-milling time further was preferably 1.5～10 hours more than 1 hour after the middle adding of step (1 ') carbon source, was preferably 2～6 hours especially;
Preferably, wet-milling described in the step (1) is wet-milling while stirring, particularly preferably in ball milling while stirring in the agitating ball mill;
Preferably, add in the step (1 ') before the carbon source and/or said afterwards wet-milling is wet-milling while stirring, particularly preferably in ball milling while stirring in the agitating ball mill.
8. like each described method of claim 1-7, it is characterized in that the ball milling time described in the step (2) was preferably more than 1 hour, further was preferably 1.5～20 hours, was preferably 2～16 hours especially;
Preferably, ball milling described in the step (2) carries out drying after finishing, and obtains nanometer fibrous lithium manganese phosphate presoma, especially preferably after the drying equipment intensive drying, obtains nanometer fibrous lithium manganese phosphate presoma; Preferably, said drying equipment is a kind or at least 2 kinds combination in turning circle cartridge type drying machine, pneumatic drier, vacuum drying chamber, the air dry oven;
Preferably, protective atmosphere is inert gas or weakly reducing atmosphere described in the step (3); Preferred especially, said inert gas or weakly reducing atmosphere be argon gas, nitrogen, added a kind or at least 2 kinds combination in the gaseous mixture of nitrogen and/or argon gas of hydrogen; Preferably, the addition of said hydrogen is mark 0.1～10% by volume, further is preferably 0.5～8%, is preferably 1～5% especially; Preferably, said nitrogen and/or argon gas are high-purity gas.
9. like each described method of claim 1-7, it is characterized in that the heat treatment programming rate is preferably below 40 ℃/minute described in the step (3), further be preferably 1～30 ℃/minute, be preferably 2～20 ℃/minute especially;
Preferably, heat treatment described in the step (3) is carried out with 100～550 ℃ and 550～1100 ℃ of two temperature sections successively; Preferably, first temperature section is 150～520 ℃, is preferably 200～500 ℃ especially; Preferably, second temperature section is 580～1000 ℃, is preferably 600～900 ℃ especially; Preferably, said two temperature sections all are temperature constant state; Preferably, said first temperature section heat treatment time is more than 1 hour, further is preferably more than 2 hours, is preferably 3～10 hours especially; Preferably, said second temperature section heat treatment time is more than 2 hours, further is preferably more than 4 hours, is preferably 6～24 hours especially.
10. the lithium ion battery anode material manganese lithium phosphate nanofiber like each described method preparation of claim 1-9 is characterized in that said lithium manganese phosphate nanofiber diameter is less than 100nm.
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| CN103779563A (en) * | 2014-01-20 | 2014-05-07 | 重庆特瑞电池材料股份有限公司 | Method for preparing copper/carbon-coated lithium iron phosphate |
| CN104241645A (en) * | 2014-04-29 | 2014-12-24 | 常州普格纳能源材料有限公司 | Synthesis method of lithium-manganese-phosphate anode material |
| CN108862229A (en) * | 2018-06-15 | 2018-11-23 | 合肥亚龙化工有限责任公司 | A kind of synthetic method of battery cathode material lithium manganese phosphate |
| CN111682202A (en) * | 2019-09-02 | 2020-09-18 | 重庆特瑞电池材料股份有限公司 | Method for synthesizing rodlike lithium iron phosphate by PVA (polyvinyl alcohol) -assisted two-fluid spraying solid phase |
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| CN111682202B (en) * | 2019-09-02 | 2022-12-27 | 重庆特瑞电池材料股份有限公司 | Method for synthesizing rodlike lithium iron phosphate by PVA (polyvinyl alcohol) -assisted two-fluid spraying solid phase |
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