CN103606678A - Preparation method of lithium manganese phosphate-conductive polymer for anode material for lithium ion battery - Google Patents

Preparation method of lithium manganese phosphate-conductive polymer for anode material for lithium ion battery Download PDF

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CN103606678A
CN103606678A CN201310660916.5A CN201310660916A CN103606678A CN 103606678 A CN103606678 A CN 103606678A CN 201310660916 A CN201310660916 A CN 201310660916A CN 103606678 A CN103606678 A CN 103606678A
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lithium
manganese
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phosphate
source compound
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左朋建
王利光
尹鸽平
马玉林
杜春雨
程新群
高云智
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Harbin Institute of Technology
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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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a preparation method of a lithium manganese phosphate-conductive polymer for an anode material for a lithium ion battery, relates to a preparation method of an anode material for a lithium ion battery, which solves the technical problem of poor conductivity of an existing lithium manganese phosphate material. The preparation method provided by the invention comprises the steps of 1. adding a lithium source compound, a phosphorus source compound and a manganese source compound into a liquid medium, then adding an additive, stirring, and regulating pH to obtain a suspension; 2. preparing a pure phase lithium manganese phosphate; 3. carrying out ball milling and mixing on the pure phase lithium manganese phosphate obtained in the step 2 and an organic carbon source compound to obtain a mixture powder; and 4. raising the temperature of the mixture powder obtained in the step 3 under the protection of inert gas for thermal treatment, and then naturally cooling to a room temperature to obtain the lithium manganese phosphate-conductive polymer. According to the preparation method, low-temperature heat treatment is adopted, the energy consumption is low, and the industrialized production is favorably realized. The preparation method is applied to the field of preparation of the anode material for the lithium ion battery.

Description

A kind of preparation method of lithium ion battery anode material manganese lithium phosphate-conduction polymer
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries.
Background technology
Lithium ion battery is as a kind of high performance green power supply of filling, in various portable type electronic products and communication tool, be used widely in recent years, and be progressively developed as the electrical source of power of electric automobile, thereby promote it to the future development of safety, environmental protection, low cost and high-energy-density.Wherein, particularly the development of positive electrode is very crucial for new electrode materials.The anode material for lithium-ion batteries of broad research concentrates on the transition metal oxide of lithium as the LiMO of layer structure at present 2the LiMn of (M=Co, Ni, Mn) and spinel structure 2o 4.But they respectively have shortcoming, LiCoO as positive electrode 2cost is high, natural resources shortage, and toxicity is large; Lithium nickelate (LiNiO 2) preparation difficulty, poor heat stability; LiMn 2o 4capacity is lower, and cyclical stability especially high-temperature behavior is poor.In order to solve the defect of above material, people have done large quantity research, above positive electrode are being carried out to various modifications with when improving its performance, and the exploitation of novel anode material is also the emphasis of paying close attention to always.Research is found, lithium manganese phosphate material operating voltage moderate (4.1V), the high 171mAh/g of theoretical capacity, good cycle, cost is very low, and its energy density is higher by 34% than LiFePO 4, its high-energy-density and high safety performance make it in power lithium-ion battery, have outstanding application prospect, and weak point is its electric conductivity difference.
Mostly adopt at present the method for bag carbon to improve its conductivity, generally use if the compounds such as glucose, sucrose are as carbon source, such carbon source promotes limited to its conductivity, and the organic compounds such as phenolic resins and aromatic compound can form the two dimensional surface polymeric material that class π key forms under suitable heat treatment temperature, by the finishing of this type of material, can promote greatly its conductivity and stability, and then improve its chemical property, and the method energy consumption is low, process conditions are easy to control, are conducive to realize suitability for industrialized production.
Summary of the invention
The present invention is the technical problem that will solve the electric conductivity difference of existing lithium manganese phosphate material, thereby a kind of preparation method of lithium ion battery anode material manganese lithium phosphate-conduction polymer is provided.
The preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer of the present invention carries out according to the following steps:
One, Li source compound, P source compound and manganese source compound are joined in liquid medium, the additive then adding, stirs 4h～5h, regulates pH to 5～7, obtains suspension-turbid liquid; Wherein, the mol ratio of Li source compound, P source compound and manganese source compound is 1～3:1:1; The mol ratio of liquid medium, additive and manganese source compound is 1:0.01～0.05:0.01～0.1;
Two, the suspension-turbid liquid that step 1 is obtained is transferred in the reactor of tetrafluoroethene, airtight, at 160 ℃～240 ℃, be incubated after 3h～24h, be cooled to room temperature, take out and generate liquid, after elimination supernatant, add distilled water to carry out sonic oscillation, then centrifugal 5min～10min under the rotating speed of 6000r/min～8000r/min, after elimination supernatant liquor, again add distilled water to carry out sonic oscillation centrifugal, be repeated to solution colour transparent, then elimination supernatant, add ethanol, repeat vibration and centrifugal process, transparent to solution colour, take out precipitation, at 50 ℃～100 ℃, being incubated 12h～24h dries, obtain pure phase lithium manganese phosphate,
Three, pure phase lithium manganese phosphate step 2 being obtained and organic carbon source compound are ball milling 1h～20h under 100r/min～800r/min at rotational speed of ball-mill, obtain mix powder;
Four, mix powder step 3 being obtained is warming up at 200 ℃～700 ℃ and heat-treats 1h～20h under inert gas shielding, then naturally cools to room temperature, obtains lithium manganese phosphate-conduction polymer; Wherein, heating rate is 1 ℃/min～20 ℃/min.
The present invention includes following beneficial effect:
1, the prepared pure phase lithium manganese phosphate particle size of this method is controlled, between 200nm～400nm, evenly, better dispersed;
2, mechanical milling process can further dwindle particle size, improves the chemical property of material, and mechanical milling process can make organic substance carbon source be coated on uniformly pure phase lithium manganese phosphate surface, improves the conductivity of material;
3, adopt the staggered structure of this five-membered ring and hexatomic ring (as doping type polyacene PAS) to can greatly improve conductivity and the stability of material, improve its multiplying power and cyclical stability, improve the reversible capacity of material;
4, preparation process of the present invention is simple, is easy to control, and pollution-free, cost is low, adopts Low Temperature Heat Treatment, and energy consumption is low, is conducive to realize suitability for industrialized production;
5, lithium manganese phosphate-conduction polymer composite material that prepared by the present invention has very high practical value, and the present invention not only can be used for manganese-lithium phosphate anode material, also can be used for other and need be coated the material that improves conductivity.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of pure phase lithium manganese phosphate LMP of test one preparation and the XRD diffraction pattern of the standard card of lithium manganese phosphate LMP; Wherein, the XRD diffraction pattern of the 1 pure phase lithium manganese phosphate LMP for test one preparation, 2 is the XRD diffraction pattern of the standard card of lithium manganese phosphate LMP;
Fig. 2 is the SEM photo of the pure phase lithium manganese phosphate LMP of test one preparation;
Fig. 3 is the SEM photo of the pure phase lithium manganese phosphate LMP-doping type PAS composite material of test one preparation;
The first discharge curve of the pure phase lithium manganese phosphate LMP-doping type PAS composite material that Fig. 4 is test one preparation when different multiplying; Wherein, 1 discharge curve first while being 0.1C; 2 discharge curves first while being 0.5C; 3 discharge curves first while being 1C; 4 discharge curves first while being 5C.
Embodiment
Embodiment one; The preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer of present embodiment carries out according to the following steps:
One, Li source compound, P source compound and manganese source compound are joined in liquid medium, the additive then adding, stirs 4h～5h, regulates pH to 5～7, obtains suspension-turbid liquid; Wherein, the mol ratio of Li source compound, P source compound and manganese source compound is 1～3:1:1; The mol ratio of liquid medium, additive and manganese source compound is 1:0.01～0.05:0.01～0.1;
Two, the suspension-turbid liquid that step 1 is obtained is transferred in the reactor of tetrafluoroethene, airtight, at 160 ℃～240 ℃, be incubated after 3h～24h, be cooled to room temperature, take out and generate liquid, after elimination supernatant, add distilled water to carry out sonic oscillation, then centrifugal 5min～10min under the rotating speed of 6000r/min～8000r/min, after elimination supernatant liquor, again add distilled water to carry out sonic oscillation centrifugal, be repeated to solution colour transparent, then elimination supernatant, add ethanol, repeat vibration and centrifugal process, transparent to solution colour, take out precipitation, at 50 ℃～100 ℃, being incubated 12h～24h dries, obtain pure phase lithium manganese phosphate,
Three, pure phase lithium manganese phosphate step 2 being obtained and organic carbon source compound are ball milling 1h～20h under 100r/min～800r/min at rotational speed of ball-mill, obtain mix powder;
Four, mix powder step 3 being obtained is warming up to 200 ℃～700 ℃ and heat-treats 1h～20h under inert gas shielding, then naturally cools to room temperature, obtains lithium manganese phosphate-conduction polymer; Wherein, heating rate is 1 ℃/min～20 ℃/min.
Present embodiment comprises following beneficial effect:
1, the prepared pure phase lithium manganese phosphate particle size of this method is controlled, between 200nm～400nm, evenly, better dispersed;
2, mechanical milling process can further dwindle particle size, improves the chemical property of material, and mechanical milling process can make organic substance carbon source be coated on uniformly pure phase lithium manganese phosphate surface, improves the conductivity of material;
3, adopt the staggered structure of this five-membered ring and hexatomic ring (as doping type polyacene PAS) to can greatly improve conductivity and the stability of material, improve its multiplying power and cyclical stability, improve the reversible capacity of material;
4, present embodiment preparation process is simple, is easy to control, and pollution-free, cost is low, adopts Low Temperature Heat Treatment, and energy consumption is low, is conducive to realize suitability for industrialized production;
5, lithium manganese phosphate-conduction polymer composite material that prepared by present embodiment has very high practical value, and the present invention not only can be used for manganese-lithium phosphate anode material, also can be used for other and need be coated the material that improves conductivity.
Embodiment two: present embodiment is different from embodiment one: in step 1, the mol ratio of Li source compound, P source compound and manganese source compound is 3:1:1.Other is identical with embodiment one.
Embodiment three: present embodiment is to carry absolutely execution mode one or two different: in step 1, microcosmic salt compound is a kind of in lithium dihydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, phosphoric acid, phosphorous acid, pyrophosphoric acid and diammonium hydrogen phosphate or two or morely mixes in any proportion.Other is identical with embodiment one or two.
Embodiment four: present embodiment is to carry absolutely one of execution mode one to three different: in step 1, lithium salt compound is a kind of in lithium carbonate, lithium acetate, lithium phosphate, phosphorous acid lithium, pyrophosphoric acid lithium, 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 and lithium sulfate or two or morely mixes in any proportion.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is to carry absolutely one of execution mode one to four different: in step 1, manganese salt compound is a kind of in manganese carbonate, manganese sulfate, manganese nitrate, manganese acetate and manganese citrate or two or morely mixes in any proportion.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is to carry absolutely one of execution mode one to five different: in step 1, liquid medium is a kind of in water, ethanol, acetone, phenmethylol, n-hexane, water-ethanol solution, water-phenmethylol, ethylene glycol or polyethylene glycol or two or morely mixes in any proportion.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is to carry absolutely one of execution mode one to six different: in step 1, additive is a kind of of ascorbic acid, citric acid, oleic acid, softex kw, benzene sulfonic acid sodium salt, PVP, neopelex, laurate, lauryl sodium sulfate and paraffin or two or morely mixes in any proportion.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is to carry absolutely one of execution mode one to seven different: in step 3, organic carbon source compound is phenolic resins, boron modified phenolic resin, phosphorus phenol-formaldehyde resin modified, metal-modified phenolic resins, Pioloform, polyvinyl acetal phenol-formaldehyde resin modified, polyamide modified phenolic resins, epoxy modified phenolic resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, dimethylbenzene phenol-formaldehyde resin modified, the new phenolic resins of modification, carbon nano-tube modification phenolic resins, benzene, naphthalene, pyridine, quinoline, metalloporphyrin, a kind of or the two or more mixing in any proportion of graphite and fullerene.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is to carry absolutely one of execution mode one to eight different: in step 4, inert atmosphere is nitrogen, argon gas or argon-hydrogen mixed gas, and wherein, in argon-hydrogen gaseous mixture, the volume content of hydrogen is 2%～10%.Other is identical with one of embodiment one to eight.
By following verification experimental verification beneficial effect of the present invention:
Test one: the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer of this test realizes according to the following steps:
One, by 1.59g LiOHH 2o, 2.0487g MnSO 4h 2o and 1.3835g H 3pO 4(85%) join in the liquid medium that 30mL water and 30mL ethanol is mixed into, then add 0.1g ascorbic acid, stir 5h, regulate pH to 6.0, obtain suspension-turbid liquid;
Two, the suspension-turbid liquid that step 1 is obtained is transferred in the reactor of tetrafluoroethene, airtight, at 200 ℃, be incubated after 10h, be cooled to room temperature, take out and generate liquid, after elimination supernatant, add distilled water to carry out sonic oscillation, then centrifugal 5min under the rotating speed of 6000r/min, after elimination supernatant liquor, again add distilled water to carry out sonic oscillation centrifugal, be repeated to solution colour transparent, then elimination supernatant, add ethanol, repeat vibration and centrifugal process, transparent to solution colour, take out precipitation, forced air drying 12h at 50 ℃, obtain pure phase lithium manganese phosphate,
The phenolic resins of the 1.6g pure phase lithium manganese phosphate three, step 2 being obtained and the modification of 0.4g boron is ball milling 5h under 300r/min at rotational speed of ball-mill, obtains mix powder;
Four, mix powder step 3 being obtained is at H 2(5%)+Ar(95%) under inert gas shielding, be warming up to 700 ℃ and heat-treat 15h, then naturally cool to room temperature, obtain lithium manganese phosphate-conduction polymer; Wherein, heating rate is 5 ℃/min.
The XRD diffraction pattern of pure phase lithium manganese phosphate LMP that this is prepared and the XRD diffraction pattern of the standard card of lithium manganese phosphate LMP are as shown in Figure 1; Wherein, the XRD diffraction pattern of the 1 pure phase lithium manganese phosphate LMP for test one preparation, 2 is the XRD diffraction pattern of the standard card of lithium manganese phosphate LMP; As can be seen from Figure 1, the pure phase lithium manganese phosphate LMP of this test preparation is lithium manganese phosphate really.
As shown in Figure 2, as can be seen from Figure 2, the particle size of the pure phase lithium manganese phosphate LMP that this is prepared is 200～400nm to the SEM photo of the pure phase lithium manganese phosphate LMP that this is prepared;
As shown in Figure 3, as can be seen from Figure 3, PAS composite material can be coated on pure phase lithium manganese phosphate surface to the SEM photo of the pure phase lithium manganese phosphate LMP-doping type PAS composite material of this test preparation uniformly;
The first discharge curve of the pure phase lithium manganese phosphate LMP-doping type PAS composite material of this test preparation when different multiplying as shown in Figure 4; Wherein, 1 discharge curve first while being 0.1C; 2 discharge curves first while being 0.5C; 3 discharge curves first while being 1C; 4 discharge curves first while being 5C; As seen from Figure 4, LMP-doping type PAS is as lithium ion anode material, when 0.1C, 0.5C, 1C and 5C, reversible capacity is respectively 161mAh/g, 127mAh/g, 117mAh/g and 71mAh/g first, during 1C electric discharge, after 500 circulations, capability retention is that after 96%, 1000 circulation, capability retention is 90%.Illustrate that LMP-doping type PAS material prepared by the present invention has excellent high rate performance, cyclical stability and good reversible capacity.
Test two: the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer of this test realizes according to the following steps:
One, by 2.385g LiOHH 2o, 3.0730g MnSO 4h 2o and 2.0752g H 3pO 4(85%) join in the liquid medium that 10mL water and 50mL phenmethylol be mixed into, then add 0.5g oleic acid, stir 4h, regulate pH to 5.5, obtain suspension-turbid liquid;
Two, the suspension-turbid liquid that step 1 is obtained is transferred in the reactor of tetrafluoroethene, airtight, at 180 ℃, be incubated after 12h, be cooled to room temperature, take out and generate liquid, after elimination supernatant, add distilled water to carry out sonic oscillation, then centrifugal 10min under the rotating speed of 7000r/min, after elimination supernatant liquor, again add distilled water to carry out sonic oscillation centrifugal, be repeated to solution colour transparent, then elimination supernatant, add ethanol, repeat vibration and centrifugal process, transparent to solution colour, take out precipitation, in 90 ℃ of vacuumize 12h, obtain pure phase lithium manganese phosphate,
Three, 1.8g pure phase lithium manganese phosphate step 2 being obtained and 0.5g pyridine are ball milling 8h under 400r/min at rotational speed of ball-mill, obtain mix powder;
Four, mix powder step 3 being obtained is at H 2(5%)+Ar(95%) under inert gas shielding, be warming up to 500 ℃ and heat-treat 20h, then naturally cool to room temperature, obtain lithium manganese phosphate-conduction polymer; Wherein, heating rate is 10 ℃/min.
When lithium manganese phosphate-conduction polymer composite material 1C of this test preparation discharges, reversible capacity is 120mAh/g first, and after 300 circulations, capability retention is 90%.
Test three: the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer of this test realizes according to the following steps:
One, by 1.06g LiOHH 2o, 1.3658g MnSO 4h 2o and 0.9233g H 3pO 4(85%) join in the liquid medium that 50mL water and 10mL ethylene glycol is mixed into, then add 0.8g ascorbic acid, stir 5h, regulate pH to 7.0, obtain suspension-turbid liquid;
Two, the suspension-turbid liquid that step 1 is obtained is transferred in the reactor of tetrafluoroethene, airtight, at 160 ℃, be incubated after 24h, be cooled to room temperature, take out and generate liquid, after elimination supernatant, add distilled water to carry out sonic oscillation, then centrifugal 8min under the rotating speed of 8000r/min, after elimination supernatant liquor, again add distilled water to carry out sonic oscillation centrifugal, be repeated to solution colour transparent, then elimination supernatant, add ethanol, repeat vibration and centrifugal process, transparent to solution colour, take out precipitation, vacuumize 12h at 100 ℃, obtain pure phase lithium manganese phosphate,
Three, 1.5g pure phase lithium manganese phosphate step 2 being obtained and 0.3g naphthalene are ball milling 5h under 350r/min at rotational speed of ball-mill, obtain mix powder;
Four, mix powder step 3 being obtained is at H 2(5%)+Ar(95%) under inert gas shielding, be warming up to 350 ℃ and heat-treat 12h, then naturally cool to room temperature, obtain lithium manganese phosphate-conduction polymer; Wherein, heating rate is 3 ℃/min.
When lithium manganese phosphate-conduction polymer composite material 0.1C of this test preparation discharges, reversible capacity is 160mAh/g first, and after 300 circulations, capability retention is 95%.

Claims (9)

1. a preparation method for lithium ion battery anode material manganese lithium phosphate-conduction polymer, the preparation method who it is characterized in that lithium ion battery anode material manganese lithium phosphate-conduction polymer carries out according to the following steps:
One, Li source compound, P source compound and manganese source compound are joined in liquid medium, then add additive, stir 4h～5h, regulate pH to 5～7, obtain suspension-turbid liquid; Wherein, the mol ratio of Li source compound, P source compound and manganese source compound is 1～3:1:1; The mol ratio of liquid medium, additive and manganese source compound is 1:0.01～0.05:0.01～0.1;
Two, the suspension-turbid liquid that step 1 is obtained is transferred in the reactor of tetrafluoroethene, airtight, at 160 ℃～240 ℃, be incubated after 3h～24h, be cooled to room temperature, take out and generate liquid, after elimination supernatant, add distilled water to carry out sonic oscillation, then centrifugal 5min～10min under the rotating speed of 6000r/min～8000r/min, after elimination supernatant liquor, again add distilled water to carry out sonic oscillation centrifugal, be repeated to solution colour transparent, then elimination supernatant, add ethanol, repeat vibration and centrifugal process, transparent to solution colour, take out precipitation, at 50 ℃～100 ℃, being incubated 12h～24h dries, obtain pure phase lithium manganese phosphate,
Three, pure phase lithium manganese phosphate step 2 being obtained and organic carbon source compound are ball milling 1h～20h under 100r/min～800r/min at rotational speed of ball-mill, obtain mix powder;
Four, mix powder step 3 being obtained is warming up at 200 ℃～700 ℃ and heat-treats 1h～20h under inert gas shielding, then naturally cools to room temperature, obtains lithium manganese phosphate-conduction polymer; Wherein, heating rate is 1 ℃/min～20 ℃/min.
2. the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer according to claim 1, the mol ratio that it is characterized in that Li source compound in step 1, P source compound and manganese source compound is 3:1:1.
3. the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer according to claim 1 and 2, is characterized in that in step 1, microcosmic salt compound is a kind of or two or more mixing in any proportion in lithium dihydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide, phosphoric acid, phosphorous acid, pyrophosphoric acid and diammonium hydrogen phosphate.
4. the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer according to claim 1 and 2, is characterized in that in step 1, lithium salt compound is a kind of or two or more mixing in any proportion in lithium carbonate, lithium acetate, lithium phosphate, phosphorous acid lithium, pyrophosphoric acid lithium, 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 and lithium sulfate.
5. the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer according to claim 1 and 2, is characterized in that in step 1, manganese salt compound is a kind of or two or more mixing in any proportion in manganese carbonate, manganese sulfate, manganese nitrate, manganese acetate and manganese citrate.
6. the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer according to claim 1, is characterized in that in step 1, liquid medium is a kind of or two or more mixing in any proportion in water, ethanol, acetone, phenmethylol, n-hexane, ethanolic solution, phenmethylol, ethylene glycol or polyethylene glycol.
7. the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer according to claim 1, is characterized in that in step 1, additive is a kind of or two or more mixing in any proportion of ascorbic acid, citric acid, oleic acid, softex kw, benzene sulfonic acid sodium salt, PVP, neopelex, laurate, lauryl sodium sulfate and paraffin.
8. the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer according to claim 1, it is characterized in that in step 3, organic carbon source compound is phenolic resins, boron modified phenolic resin, phosphorus phenol-formaldehyde resin modified, metal-modified phenolic resins, Pioloform, polyvinyl acetal phenol-formaldehyde resin modified, polyamide modified phenolic resins, epoxy modified phenolic resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, dimethylbenzene phenol-formaldehyde resin modified, the new phenolic resins of modification, carbon nano-tube modification phenolic resins, benzene, naphthalene, pyridine, quinoline, metalloporphyrin, a kind of or the two or more mixing in any proportion of graphite and fullerene.
9. the preparation method of a kind of lithium ion battery anode material manganese lithium phosphate-conduction polymer according to claim 1, it is characterized in that in step 4, inert atmosphere is nitrogen, argon gas or argon-hydrogen mixed gas, wherein, in argon-hydrogen gaseous mixture, the volume content of hydrogen is 2%～10%.
CN201310660916.5A 2013-12-09 2013-12-09 Preparation method of lithium manganese phosphate-conductive polymer for anode material for lithium ion battery Pending CN103606678A (en)

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CN107473197A (en) * 2017-09-08 2017-12-15 绵阳梨坪科技有限公司 A kind of preparation method for improving battery performance ferrous phosphate doping lithium material
CN107942250A (en) * 2017-09-30 2018-04-20 武汉昊诚能源科技有限公司 A kind of method of quick measurement Clock battery capacity
CN109411715A (en) * 2018-09-14 2019-03-01 华南理工大学 A kind of high-performance lithium iron manganese phosphate anode material and preparation method thereof
CN110600701A (en) * 2019-09-18 2019-12-20 湖南大学 Lithium ion battery LiMnPO4Preparation method of positive electrode carbon coating

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CN107942250B (en) * 2017-09-30 2019-12-13 武汉昊诚能源科技有限公司 method for rapidly measuring capacity of clock battery
CN109411715A (en) * 2018-09-14 2019-03-01 华南理工大学 A kind of high-performance lithium iron manganese phosphate anode material and preparation method thereof
CN110600701A (en) * 2019-09-18 2019-12-20 湖南大学 Lithium ion battery LiMnPO4Preparation method of positive electrode carbon coating

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