CN105742610B - A kind of preparation method of carbon coating lithium ferric manganese phosphate film-type positive electrode - Google Patents

A kind of preparation method of carbon coating lithium ferric manganese phosphate film-type positive electrode Download PDF

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CN105742610B
CN105742610B CN201610287296.9A CN201610287296A CN105742610B CN 105742610 B CN105742610 B CN 105742610B CN 201610287296 A CN201610287296 A CN 201610287296A CN 105742610 B CN105742610 B CN 105742610B
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lithium
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manganese phosphate
ferric manganese
positive electrode
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CN105742610A (en
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彭家兴
汪伟伟
刘兴亮
马守龙
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy 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
    • H01M4/362—Composites
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • 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
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    • 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
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    • 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
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    • 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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/625—Carbon or graphite
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Abstract

The present invention provides a kind of preparation method of carbon coating lithium ferric manganese phosphate film-type positive electrode, first carries out sanding and polishing, cleaning, drying to ferromanganese material；It is cathode by anode, stainless steel substrates of basis material, they is immersed to progress differential arc oxidation processing in micro-arc oxidation electrolyte simultaneously, one layer of phosphoric acid ferrimanganic with microcellular structure of uniform fold on substrate material surface；Lithium source is added in absolute ethyl alcohol, using graphite as anode, using the basis material for being coated with phosphoric acid ferrimanganic as cathode, carries out electrophoretic deposition under the conditions of voltage is 20 60V, lithium, which is deposited on phosphoric acid ferrimanganic, obtains lithium ferric manganese phosphate presoma；By carbon source by the method for chemical vapor deposition by Carbon deposition on lithium ferric manganese phosphate presoma, obtain carbon coating lithium ferric manganese phosphate film-type positive electrode.The present invention is easy to operate, it is easy to accomplish, the positive electrode prepared further increases energy density under the premise of keeping long life and safety.

Description

A kind of preparation method of carbon coating lithium ferric manganese phosphate film-type positive electrode
Technical field：
The present invention relates to technical field of lithium ion, more particularly, to a kind of carbon coating lithium ferric manganese phosphate film-type anode The preparation method of material.
Background technology：
Lithium ion battery has higher energy density relative to other existing common accumulators, specifically has higher Volume energy density, thus be widely used in each electrical equipment in family life, or even in the electrification of automobile In also begin to show up prominently.
With fossil energy scarcity and earth air environment it is continuous worsening, development cleaning, fuel-economizing new-energy automobile Extremely important strategic position has been put by every country.And the lithium ion in automotive interior as a source of power can be used Battery is also just at the research topic of hot spot the most.However as the progress of the advance and science and technology in epoch, electronic product, electronic vapour Requirement of the fields such as vehicle, Medical Devices and space flight and aviation to energy storage device increasingly improves, requirement of the people to lithium ion battery Higher and higher, specifically at present to the policy of new-energy automobile, the technical requirement to power battery is even more to compel in China In the eyebrows and eyelashes.
Reach the required technical indicator of existing power battery if necessary, then battery must be made to have three aspects excellent Gesture：First security performance is superior, does not generate heat in extreme collision puncture on fire；Second high-energy density, at present in the world The pure electric automobile developed, which fills primary electricity, can only at most run 200~300km, if we can improve battery energy density, more More promotion electric automobile during traveling mileage, then will more there is market prospects；Third service life, longer cycle life is not The quality of electric vehicle is only represent, and reduces somewhat use cost.From it is above-mentioned it is several from the aspect of, it is existing In power lithium battery positive electrode ternary material, LiMn2O4, LiFePO4, nickel-cobalt-manganese ternary has high-energy density and low temperature properties Can, and the Ni cation mixings for also having original service life, but being be easy to cause in poor in safety and high temperature The defect of high temperature circulation is caused to limit performance of the material on power lithium battery；LiMn2O4 LiMn2O4It is most excellent in cost Gesture, but since energy density is relatively low, incident disproportionated reaction, also Jahn-teller effects greatly reduce material Cyclical stability.And at present in the highest LiFePO of pure electric automobile occupation rate of market4Material has safety the most outstanding Can be with the cycle life of overlength, but energy density cannot reach requirement.
But another material in phosphate of olivine type material causes ours note that being exactly LiMnPO4, this Kind material has higher platform voltage 4.1V in the case where maintaining the theoretical capacity of LiFePO4, brings higher in this way Energy density, compare LiFePO4The energy density of materials theory 580Wh/kg, LiMnPO4Energy density can approach 700Wh/kg.And this system material stable structure has preferable security performance.It is considered as more promising lithium Electric positive electrode.
But LiMnPO4Also there are its inherent defect, LiMnPO4Have and compares LiFePO4Lower conductivity, since structure is led The one-dimensional ion diffusion admittance caused so that material is all very undesirable on high rate performance and cycle performance.And it uses at present traditional Material with carbon-coated surface and reduction grain graininess also cannot all improve this material property well.
Based on the above issues, the advantages of how integrating two kinds of storerooms of LiFePO4 and LiMnPO4 is allowed to keeping following Material energy densities are promoted as far as possible under the premise of ring, high rate performance, it will be as urgent technical need.
Invention content：
The object of the present invention is to provide a kind of preparation methods of carbon coating lithium ferric manganese phosphate film-type positive electrode.
Technical scheme is as follows：A kind of preparation method of carbon coating lithium ferric manganese phosphate film-type positive electrode, packet Include following steps：
（1）The pretreatment of basis material：It is cleaned, dry to obtain surface light after the processing of ferromanganese material sanding and polishing Sliding clean basis material；
（2）The preparation of ferric phosphate manganese film：Using basis material as anode, stainless steel substrates are cathode, they are immersed simultaneously It is stirred in micro-arc oxidation electrolyte, differential arc oxidation processing, i.e., one layer of uniform fold has micropore on substrate material surface The phosphoric acid ferrimanganic of structure, the basis material of phosphoric acid ferrimanganic must be coated with through rinsing, drying；
（3）The preparation of lithium ferric manganese phosphate presoma：It is 0.5- that lithium source, which is added in absolute ethyl alcohol, and is made into molar concentration The solution of 5mol/L；Then it is 20-60V in voltage to be coated with the basis material of phosphoric acid ferrimanganic as cathode using graphite as anode Under the conditions of carry out electrophoretic deposition, lithium, which is deposited on phosphoric acid ferrimanganic, obtains lithium ferric manganese phosphate presoma；
（4）By carbon source by the method for chemical vapor deposition by Carbon deposition on lithium ferric manganese phosphate presoma, calcination obtains Carbon coating lithium ferric manganese phosphate film-type positive electrode.
Further scheme, the step（1）The molar ratio of ferrimanganic is 1 in middle ferromanganese：(1-9).
Further scheme, the step（1）In cleaning be then to be sequentially placed into respectively after first being cleaned up with deionized water It is cleaned by ultrasonic 15-30min in acetone, absolute ethyl alcohol, hydrochloric acid, deionized water；The drying refers to 60~80 DEG C in drying box Dry 2~8h.
Further scheme, the step（2）Middle micro-arc oxidation electrolyte contains tertiary sodium phosphate and sodium hydroxide, wherein phosphoric acid A concentration of 0.05-0.25mol/L of trisodium, a concentration of 0.02-0.1mol/L of sodium hydroxide.
Further scheme, the step（2）The response voltage of middle differential arc oxidation processing is 60-350V, reaction time 1- 40min。
Further scheme, the step（3）Middle lithium source be lithium hydroxide, lithium nitrate, lithium acetate it is one or more.
Further scheme, the step（4）In carbon source be toluene, propylene, ethyl alcohol it is one or more.
Further scheme, the step（4）In the current-carrying gas of chemical vapor deposition be high pure nitrogen, in high-purity argon gas One kind, the mechanism of the calcining is 400-500 DEG C of heat preservation 1-10h, then is warming up to 650-900 DEG C of heat preservation 5-20h.
The excellent of LiFePO4 and lithium manganese phosphate material is combined through the carbon coating film-type lithium ferric manganese phosphate for preparing of the present invention Point, the positive electrode that can be used as lithium ion battery are used, are further increased under the premise of keeping long life and safety Energy density.
Description of the drawings
Fig. 1 is the X-ray diffractogram of carbon coating lithium ferric manganese phosphate film-type positive electrode prepared by the embodiment of the present invention 1 Spectrum；
Fig. 2 is the battery made by the carbon coating lithium ferric manganese phosphate film-type positive electrode that is prepared by the embodiment of the present invention 1 Charging and discharging curve figure.
Specific implementation mode：
The content of present invention for ease of understanding, with reference to example, the invention will be further described, but following embodiment is only Do not include whole embodiments for a part of the embodiment of the present invention：
Embodiment 1
Step 1：The pretreatment of basis material：It is 1 by ferrimanganic ratio：4 ferromanganese is processed into required shape or size And sanding and polishing processing is done, after being cleaned up with deionized water, then it is respectively placed in acetone, absolute ethyl alcohol, hydrochloric acid, deionized water It is cleaned by ultrasonic 15min, is put into 80 DEG C of drying 2h in drying box, obtains the smooth clean basis material in surface；
Step 2：Prepare micro-arc oxidation electrolyte：By tertiary sodium phosphate（A concentration of 0.05mol/L）, sodium hydroxide（It is a concentration of 0.02mol/L）It is hybridly prepared into micro-arc oxidation electrolyte；
Step 3：The preparation of ferric phosphate manganese film：Using pretreated basis material as anode, stainless steel substrates are cathode, together When immerse step 2 obtained by micro-arc oxidation electrolyte in, stirring, at room temperature carry out differential arc oxidation processing, response voltage 60- 180V（Wherein 60V is fluctuation voltage, and as ferric phosphate manganese film thickens, voltage persistently rises, and finally tends towards stability）, reaction Time is 25min, to one layer of phosphoric acid ferrimanganic with microcellular structure of uniform fold on substrate material surface, after reaction Anode is rinsed, it is spare after dry；
Step 4：The preparation of lithium ferric manganese phosphate presoma：Lithium hydroxide is added in absolute ethyl alcohol, 1.3mol/L is made into Solution, using basis material of the surface made from step 3 with phosphoric acid ferrimanganic as cathode, be in voltage and using graphite as anode Electrophoretic deposition under the conditions of 32V, at this point, the substance deposited on cathode is lithium ferric manganese phosphate presoma；
Step 5：By toluene by way of chemical vapor deposition by Carbon deposition in step（4）Before the lithium ferric manganese phosphate of preparation It drives on body, current-carrying gas is high pure nitrogen, and calcining machine is made as 400 DEG C of pre-burning 7h, then is warming up to 650 DEG C of calcining 20h and obtains carbon packet Cover lithium ferric manganese phosphate film-type positive electrode.
The X-ray diffractogram of the carbon coating lithium ferric manganese phosphate film-type positive electrode prepared as shown in Figure 1 for the present embodiment 1 Spectrum, it will be seen from figure 1 that it is consistent with the base peak of lithium ferric manganese phosphate by substance made from this method, illustrate substance obtained For lithium ferric manganese phosphate.
It is illustrated in figure 2 the battery made by the carbon coating lithium ferric manganese phosphate film-type positive electrode of the preparation of the present embodiment 1 Charging and discharging curve figure, figure it is seen that by this method prepare positive electrode have good chemical property.
Embodiment 2
Step 1：The pretreatment of basis material：It is 1 by ferrimanganic ratio：4 ferromanganese is processed into required shape or size And sanding and polishing processing is done, after being cleaned up with deionized water, then it is respectively placed in acetone, absolute ethyl alcohol, hydrochloric acid, deionized water and surpasses Sound cleans 15min, is put into 80 DEG C of drying 2h in drying box, obtains the smooth clean basis material in surface；
Step 2：Prepare micro-arc oxidation electrolyte：By tertiary sodium phosphate（A concentration of 0.05mol/L）, sodium hydroxide（It is a concentration of 0.02mol/L）It is hybridly prepared into micro-arc oxidation electrolyte；
Step 3：The preparation of ferric phosphate manganese film：Using pretreated basis material as anode, stainless steel substrates are cathode, together When immerse step 2 obtained by micro-arc oxidation electrolyte in, stirring, at room temperature carry out differential arc oxidation processing, response voltage 60- 180V（60V is fluctuation voltage, and as ferric phosphate manganese film thickens, voltage persistently rises, and finally tends towards stability）, the reaction time It after reaction will be positive to one layer of phosphoric acid ferrimanganic with microcellular structure of uniform fold on substrate material surface for 25min Pole is rinsed, spare after dry；
Step 4：The preparation of lithium ferric manganese phosphate presoma：Lithium hydroxide is added in absolute ethyl alcohol, 1.3mol/L is made into Solution, using basis material of the surface made from step 3 with phosphoric acid ferrimanganic as cathode, be in voltage and using graphite as anode Electrophoretic deposition under the conditions of 32V, at this point, the substance deposited on cathode is lithium ferric manganese phosphate presoma；
Step 5：By toluene and ethyl alcohol by way of chemical vapor deposition by Carbon deposition in step（4）The ferric phosphate of preparation On manganese lithium presoma, current-carrying gas is high pure nitrogen, and calcining machine is made as 450 DEG C of pre-burning 5h, then is warming up to 750 DEG C of calcining 16h and obtains To carbon coating lithium ferric manganese phosphate film-type positive electrode.
Embodiment 3
Step 1：The pretreatment of basis material：It is 1 by ferrimanganic ratio：9 ferromanganese is processed into required shape or size And sanding and polishing processing is done, after being cleaned up with deionized water, then it is respectively placed in acetone, absolute ethyl alcohol, hydrochloric acid, deionized water and surpasses Sound cleans 15min, is put into 60 DEG C of drying 8h in drying box, obtains the smooth clean basis material in surface；
Step 2：Prepare micro-arc oxidation electrolyte：By tertiary sodium phosphate（A concentration of 0.05mol/L）, sodium hydroxide（It is a concentration of 0.02mol/L）It is hybridly prepared into micro-arc oxidation electrolyte；
Step 3：The preparation of ferric phosphate manganese film：Using pretreated basis material as anode, stainless steel substrates are cathode, together When immerse step 2 obtained by micro-arc oxidation electrolyte in, stirring, at room temperature carry out differential arc oxidation processing, response voltage 60- 120V（60V is fluctuation voltage, and as ferric phosphate manganese film thickens, voltage persistently rises, and finally tends towards stability）, the reaction time It after reaction will be positive to one layer of phosphoric acid ferrimanganic with microcellular structure of uniform fold on substrate material surface for 40min Pole is rinsed, spare after dry；
Step 4：The preparation of lithium ferric manganese phosphate presoma：Lithium hydroxide is added in absolute ethyl alcohol, 0.5mol/L is made into Solution, using basis material of the surface made from step 3 with phosphoric acid ferrimanganic as cathode, be in voltage and using graphite as anode Electrophoretic deposition under the conditions of 20V, at this point, the substance deposited on cathode is lithium ferric manganese phosphate presoma；
Step 5：By toluene by way of chemical vapor deposition by Carbon deposition in step（4）Before the lithium ferric manganese phosphate of preparation It drives on body, current-carrying gas is high pure nitrogen, and calcining machine is made as 400 DEG C of pre-burning 10h, then is warming up to 900 DEG C of calcining 5h and obtains carbon packet Cover lithium ferric manganese phosphate film-type positive electrode.
Embodiment 4
Step 1：The pretreatment of basis material：It is 1 by ferrimanganic ratio：1 ferromanganese is processed into required shape or size And sanding and polishing processing is done, after being cleaned up with deionized water, then it is respectively placed in acetone, absolute ethyl alcohol, hydrochloric acid, deionized water and surpasses Sound cleans 30min, is put into 80 DEG C of drying 2h in drying box, obtains the smooth clean basis material in surface；
Step 2：Prepare micro-arc oxidation electrolyte：By tertiary sodium phosphate（A concentration of 0.25mol/L）, sodium hydroxide（It is a concentration of 0.1mol/L）It is hybridly prepared into micro-arc oxidation electrolyte；
Step 3：The preparation of ferric phosphate manganese film：Using pretreated basis material as anode, stainless steel substrates are cathode, together When immerse step 2 obtained by micro-arc oxidation electrolyte in, stirring, at room temperature carry out differential arc oxidation processing, response voltage 60- 350V（60V is fluctuation voltage, and as ferric phosphate manganese film thickens, voltage persistently rises, and finally tends towards stability）, the reaction time It after reaction will be positive to one layer of phosphoric acid ferrimanganic with microcellular structure of uniform fold on substrate material surface for 1min Pole is rinsed, spare after dry；
Step 4：The preparation of lithium ferric manganese phosphate presoma：Lithium hydroxide is added in absolute ethyl alcohol, is made into 5mol/L's Solution, and be 60V in voltage using basis material of the surface made from step 3 with phosphoric acid ferrimanganic as cathode using graphite as anode Under the conditions of electrophoretic deposition, at this point, the substance deposited on cathode is lithium ferric manganese phosphate presoma；
Step 5：By toluene by way of chemical vapor deposition by Carbon deposition in step（4）Before the lithium ferric manganese phosphate of preparation It drives on body, current-carrying gas is high pure nitrogen, and calcining machine is made as 500 DEG C of pre-burning 1h, then is warming up to 650 DEG C of calcining 20h and obtains carbon packet Cover lithium ferric manganese phosphate film-type positive electrode.
Embodiment 5
Step 1：The pretreatment of basis material：It is 1 by ferrimanganic ratio：4 ferromanganese is processed into required shape or size And sanding and polishing processing is done, after being cleaned up with deionized water, then it is respectively placed in acetone, absolute ethyl alcohol, hydrochloric acid, deionized water and surpasses Sound cleans 15min, is put into 80 DEG C of drying 2h in drying box, obtains the smooth clean basis material in surface；
Step 2：Prepare micro-arc oxidation electrolyte：By tertiary sodium phosphate（A concentration of 0.05mol/L）, sodium hydroxide（It is a concentration of 0.02mol/L）It is hybridly prepared into micro-arc oxidation electrolyte；
Step 3：The preparation of ferric phosphate manganese film：Using pretreated basis material as anode, stainless steel substrates are cathode, together When immerse step 2 obtained by micro-arc oxidation electrolyte in, stirring, at room temperature carry out differential arc oxidation processing, response voltage 60- 180V（60V is fluctuation voltage, and as ferric phosphate manganese film thickens, voltage persistently rises, and finally tends towards stability）, the reaction time It after reaction will be positive to one layer of phosphoric acid ferrimanganic with microcellular structure of uniform fold on substrate material surface for 25min Pole is rinsed, spare after dry；
Step 4：The preparation of lithium ferric manganese phosphate presoma：Lithium hydroxide and lithium acetate are added in absolute ethyl alcohol, are made into The solution of 1.3mol/L, and using graphite as anode, using basis material of the surface made from step 3 with phosphoric acid ferrimanganic as cathode, Electrophoretic deposition under the conditions of voltage is 32V, at this point, the substance deposited on cathode is lithium ferric manganese phosphate presoma；
Step 5：By toluene by way of chemical vapor deposition by Carbon deposition in step（4）Before the lithium ferric manganese phosphate of preparation It drives on body, current-carrying gas is high pure nitrogen, and calcining machine is made as 450 DEG C of pre-burning 5h, then is warming up to 750 DEG C of calcining 16h and obtains carbon packet Cover lithium ferric manganese phosphate film-type positive electrode.
Embodiment 6
Step 1：The pretreatment of basis material：It is 1 by ferrimanganic ratio：4 ferromanganese is processed into required shape or size And sanding and polishing processing is done, after being cleaned up with deionized water, then it is respectively placed in acetone, absolute ethyl alcohol, hydrochloric acid, deionized water and surpasses Sound cleans 15min, is put into 80 DEG C of drying 2h in drying box, obtains the smooth clean basis material in surface；
Step 2：Prepare micro-arc oxidation electrolyte：By tertiary sodium phosphate（A concentration of 0.05mol/L）, sodium hydroxide（It is a concentration of 0.02mol/L）It is hybridly prepared into micro-arc oxidation electrolyte；
Step 3：The preparation of ferric phosphate manganese film：Using pretreated basis material as anode, stainless steel substrates are cathode, together When immerse step 2 obtained by micro-arc oxidation electrolyte in, stirring, at room temperature carry out differential arc oxidation processing, response voltage 60- 180V（60V is fluctuation voltage, and as ferric phosphate manganese film thickens, voltage persistently rises, and finally tends towards stability）, the reaction time It after reaction will be positive to one layer of phosphoric acid ferrimanganic with microcellular structure of uniform fold on substrate material surface for 25min Pole is rinsed, spare after dry；
Step 4：The preparation of lithium ferric manganese phosphate presoma：Lithium nitrate is added in absolute ethyl alcohol, is made into 1.3mol/L's Solution, and be 32V in voltage using basis material of the surface made from step 3 with phosphoric acid ferrimanganic as cathode using graphite as anode Under the conditions of electrophoretic deposition, at this point, the substance deposited on cathode is lithium ferric manganese phosphate presoma；
Step 5：By toluene by way of chemical vapor deposition by Carbon deposition in step（4）Before the lithium ferric manganese phosphate of preparation It drives on body, current-carrying gas is high pure nitrogen, and calcining machine is made as 450 DEG C of pre-burning 5h, then is warming up to 750 DEG C of calcining 16h and obtains carbon packet Cover lithium ferric manganese phosphate film-type positive electrode.
Above content is only the structure example and explanation to the present invention, affiliated those skilled in the art It makes various modifications or additions to the described embodiments or substitutes by a similar method, without departing from this hair Bright structure or beyond the scope defined by this claim, is within the scope of protection of the invention.

Claims (7)

1. a kind of preparation method of carbon coating lithium ferric manganese phosphate film-type positive electrode, it is characterised in that：Include the following steps：
（1）The pretreatment of basis material：After the processing of ferromanganese material sanding and polishing, it is cleaned, dry surface is smooth dry Net basis material；
（2）The preparation of ferric phosphate manganese film：Using basis material as anode, stainless steel substrates are cathode, they are immersed the differential of the arc simultaneously It is stirred in oxidation electrolyte, differential arc oxidation processing, i.e., one layer of uniform fold has microcellular structure on substrate material surface Phosphoric acid ferrimanganic, the basis material for being coated with phosphoric acid ferrimanganic is obtained through rinsing, drying；
（3）The preparation of lithium ferric manganese phosphate presoma：It is 0.5-5mol/L that lithium source, which is added in absolute ethyl alcohol, and is made into molar concentration Solution；Then using graphite as anode, to be coated with the basis material of phosphoric acid ferrimanganic as cathode, under the conditions of voltage is 20-60V Electrophoretic deposition is carried out, lithium, which is deposited on phosphoric acid ferrimanganic, obtains lithium ferric manganese phosphate presoma；
（4）By carbon source by the method for chemical vapor deposition by Carbon deposition on lithium ferric manganese phosphate presoma, carbon is obtained after calcining Coat lithium ferric manganese phosphate film-type positive electrode；
The step（2）Middle micro-arc oxidation electrolyte contains tertiary sodium phosphate and sodium hydroxide, and wherein tertiary sodium phosphate is a concentration of 0.05-0.25mol/L, a concentration of 0.02-0.1mol/L of sodium hydroxide.
2. preparation method according to claim 1, it is characterised in that：The step（1）Ferrimanganic rubs in middle ferromanganese You are than being iron：Manganese=1：(1-9).
3. preparation method according to claim 1, it is characterised in that：The step（1）In drying refer in drying box In 60~80 DEG C drying 2~8h.
4. preparation method according to claim 1, it is characterised in that：The step（2）The reaction of middle differential arc oxidation processing Voltage is 60-350V, reaction time 1-40min.
5. preparation method according to claim 1, it is characterised in that：The step（3）Middle lithium source is lithium hydroxide, nitric acid Lithium, lithium acetate it is one or more.
6. preparation method according to claim 1, it is characterised in that：The step（4）In carbon source be toluene, propylene, Ethyl alcohol it is one or more.
7. preparation method according to claim 1, it is characterised in that：The step（4）In chemical vapor deposition load Gas body is one kind in high pure nitrogen, high-purity argon gas；The mechanism of the calcining is 400-500 DEG C of heat preservation 1-10h, then is warming up to 650-900 DEG C of heat preservation 5-20h.
CN201610287296.9A 2016-05-04 2016-05-04 A kind of preparation method of carbon coating lithium ferric manganese phosphate film-type positive electrode Active CN105742610B (en)

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