CN106328942B - A kind of lithium ferric manganese phosphate positive electrode, preparation method and application - Google Patents

A kind of lithium ferric manganese phosphate positive electrode, preparation method and application Download PDF

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CN106328942B
CN106328942B CN201610993715.0A CN201610993715A CN106328942B CN 106328942 B CN106328942 B CN 106328942B CN 201610993715 A CN201610993715 A CN 201610993715A CN 106328942 B CN106328942 B CN 106328942B
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lithium
positive electrode
source compound
manganese phosphate
manganese
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CN106328942A (en
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卢苇
王可飞
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Ningde Amperex Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

This application involves a kind of lithium ferric manganese phosphate positive electrode, chemical formula LiFe1‑xMnxPO4(0 < x < 1), is prepared using method of electrostatic spinning.The application further relates to the preparation method of the lithium ferric manganese phosphate positive electrode and the lithium ion battery using the lithium ferric manganese phosphate positive electrode.The application uses pore creating material in the preparation method of the material, obtained lithium ferric manganese phosphate positive electrode draw ratio with higher and porosity, it is capable of providing big specific surface area, keep conductive agent and active contacts site more, the formation of hole is capable of providing more diffusion admittances simultaneously, the abundant diffusion length for impregnating to reduce lithium ion for guaranteeing electrolyte, improves the conductivity of anode material for lithium-ion batteries, so as to improve the high rate performance of lithium ion battery.

Description

A kind of lithium ferric manganese phosphate positive electrode, preparation method and application
Technical field
This application involves field of lithium ion battery anode, specifically, are related to a kind of lithium ferric manganese phosphate positive electrode, Preparation method and application.
Background technique
In anode material for lithium-ion batteries, the electric conductivity of lithium ferric manganese phosphate is poor.Although nanosizing can make electrochemistry Performance is preferable, but existing preparation method such as high temperature solid-state method, sol-gal process, the methods of hydro-thermal method preparation grain diameter compared with Big and not easy to control, batch consistency is poor.Electrostatic spinning technique is one and prepares the quick, easy, easy to operate of nanofiber And various informative technology, the superfine fibre of technology preparation have large specific surface area, fiber footpath is thin, and light and pattern is first-class Feature.Since there are these advantages, Electrospun is widely used in drug controlled release, dielectric film, the fields such as filtering.
It exists in the prior art and lithium iron phosphate nanofiber band and lithium iron phosphate nanofiber is prepared by method of electrostatic spinning Method.These methods are mainly started in terms of the electronic conductivity for improving LiFePO4.However how to pass through electrostatic spinning skill Art prepares lithium ferric manganese phosphate, and further increases the electronic conductivity of positive electrode nanofiber and ionic conductivity also needs It is studied.
In consideration of it, special propose the application.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of lithium ferric manganese phosphate positive electrode.
The second goal of the invention of the application is to propose the preparation method of the lithium ferric manganese phosphate positive electrode
The third goal of the invention of the application is to propose lithium ferric manganese phosphate positive electrode the answering in lithium ion battery With.
In order to complete the purpose of the application, the technical solution of use are as follows:
A kind of lithium ferric manganese phosphate positive electrode, chemical formula LiFe1-xMnxPO4(0 < x < 1), using electrostatic spinning legal system It is standby to obtain.
Preferably, the lithium ferric manganese phosphate positive electrode is nanofiber, and the diameter of the nanofiber is 0.1-0.5 μ M, surface and internal distribution hole.
The preparation method of the lithium ferric manganese phosphate positive electrode the following steps are included:
1) Li source compound, Fe source compound, manganese source compound and P source compound are dissolved in the first solvent, are obtained Precursor solution；
2) high molecular polymer and pore creating material are dissolved in the second solvent, obtain polymer solution；
3) precursor solution is mixed with the polymer solution, obtains spinning solution；
4) electrostatic spinning is carried out to the spinning solution, obtains lithium ferric manganese phosphate presoma；
5) the lithium ferric manganese phosphate presoma is sintered, obtains the lithium ferric manganese phosphate positive electrode.
Preferably, in step 1) and step 2), the Fe source compound is selected from ferric oxalate, ferrous oxalate, ferric nitrate, sulfuric acid One of ferrous ammonium, iron chloride, frerrous chloride, ferrous acetate are a variety of；The manganese source compound is selected from manganese acetate, nitric acid One of manganese, ammonium manganous sulfate, manganese carbonate, manganese oxalate are a variety of；Phosphorus source compound is selected from one hydrogen lithium of phosphoric acid, biphosphate One of lithium, monoammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, diammonium hydrogen phosphate are a variety of；The Li source compound is selected from carbon One of sour lithium, lithium hydroxide, lithium nitrate, one hydrogen lithium of phosphoric acid, lithium dihydrogen phosphate, lithium acetate are a variety of；The polyphosphazene polymer It closes object and is selected from polyvinyl formal, polyethylene glycol oxide, polyacrylonitrile, Kynoar, polyvinylpyrrolidone, poly- methyl-prop One of e pioic acid methyl ester is a variety of；First solvent and the second solvent are volatile organic solvent, are selected from ethyl alcohol, third One of ketone, chloroform, methylene chloride, N,N-dimethylformamide, N-Methyl pyrrolidone are a variety of.
Preferably, in step 1), the pore creating material is low melting point organic matter, is preferably selected from ethylene carbonate, polyethylene glycol At least one of；
Preferably, Li source compound, Fe source compound, manganese source compound, phosphorus source in step 3), in the spinning solution The dosage of compound is calculated as 1:0.2~0.8:0.2~0.8:1 by the ratio of amount of substance of lithium, iron, manganese, P elements；Polyphosphazene polymer The mass content for closing object accounts for the 1-25% of spinning solution gross mass.
Preferably, in step 3), the mass content of pore creating material accounts for the 1%- of spinning solution gross mass in the spinning solution 10%, preferably 1%-5%.
Preferably, in step 4), electrostatic spinning temperature be 5-60 DEG C, preferably 30-60 DEG C, voltage 5-60KV, solidification away from From for 10-35cm.
Preferably, in step 5), sintering atmosphere is one or more gaseous mixtures of nitrogen, argon gas, hydrogen, and sintering temperature is 500-750 DEG C, preferably 600-700 DEG C, sintering time are 5-14 hours.
A kind of lithium ion battery uses lithium ferric manganese phosphate positive electrode described herein.
The technical solution of the application at least has following beneficial effect:
This application provides a kind of lithium ferric manganese phosphate positive electrode of nanofiber grade, draw ratio with higher and hole Gap rate is capable of providing big specific surface area, and conductive agent and active contacts site are more, while the formation of hole is capable of providing More diffusion admittances guarantee the abundant diffusion length for impregnating to reduce lithium ion of electrolyte, improve lithium ion battery The conductivity of positive electrode, so as to improve the high rate performance of battery.
Present invention also provides the preparation methods of the lithium ferric manganese phosphate positive electrode.In the preferred scheme, pass through change The additional amount and amount ratio of pore creating material, can further increase the high rate performance of battery.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the application electrostatic spinning apparatus；
Wherein: 1- spinning solution；2- injection needle；3- receiver board；4- high voltage power supply.
Fig. 2 is the scanning electron microscope (SEM) photograph of positive electrode P2 in embodiment.
Fig. 3 is the structural schematic diagram of the application lithium ferric manganese phosphate material.
Fig. 4 is the charge-discharge performance test chart of battery C2 in embodiment.
Fig. 5 is the high rate performance test chart of battery C2 in embodiment.
Specific embodiment
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application Rather than limitation scope of the present application.
This application involves a kind of lithium ferric manganese phosphate positive electrode, chemical formula LiFe1-xMnxPO4(0 < x < 1), the material It is prepared using method of electrostatic spinning.Electrostatic spinning is a kind of fiber fabrication process, and substantially process is by polymer solution or to melt Body carries out jet spinning in strong electrical field, and the diameter for the polymer filaments produced is nanoscale.
In this application, for nanofiber, diameter exists the lithium ferric manganese phosphate positive electrode for using method of electrostatic spinning to obtain 0.1-0.5 μm or so.Surface and internal distribution hole due to having used pore creating material, in nanofiber.
The application further relates to the preparation method of the lithium ferric manganese phosphate positive electrode, comprising the following steps:
1) Li source compound, Fe source compound, manganese source compound, P source compound are dissolved in the first solvent, are obtained Precursor solution；
2) high molecular polymer and pore creating material are dissolved in the second solvent, obtain polymer solution；
3) precursor solution is mixed with polymer solution, obtains spinning solution；
4) electrostatic spinning is carried out to spinning solution, obtains lithium ferric manganese phosphate presoma；
5) lithium ferric manganese phosphate presoma is sintered, obtains lithium ferric manganese phosphate positive electrode.
A kind of improvement of preparation method as the application lithium ferric manganese phosphate positive electrode, in step 1) and step 2), Fe source compound is in ferric oxalate, ferrous oxalate, ferric nitrate, iron ammonium sulfate, iron chloride, frerrous chloride, ferrous acetate It is one or more；Manganese source compound is selected from one of manganese acetate, manganese nitrate, ammonium manganous sulfate, manganese carbonate, manganese oxalate or a variety of； P source compound is in one hydrogen lithium of phosphoric acid, lithium dihydrogen phosphate, monoammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, diammonium hydrogen phosphate It is one or more；Li source compound is selected from lithium carbonate, lithium hydroxide, lithium nitrate, one hydrogen lithium of phosphoric acid, lithium dihydrogen phosphate, acetic acid One of lithium is a variety of；High molecular polymer is selected from polyvinyl formal (PVFM), polyethylene glycol oxide (PEO), polypropylene One of nitrile (PAN), Kynoar (PVDF), polyvinylpyrrolidone (PVP), polymethyl methacrylate are a variety of； First solvent and the second solvent are volatile organic solvent, are selected from ethyl alcohol, acetone, chloroform, methylene chloride, N, N- dimethyl methyl One of amide (DMF), N-Methyl pyrrolidone (NMP) are a variety of.
A kind of improvement of preparation method as the application lithium ferric manganese phosphate positive electrode, due to substance each in spinning solution Exist with liquid condition, the fusing point of pore creating material should be lower than electrostatic spinning temperature.Spinning should be avoided during electrostatic spinning simultaneously High molecular polymer in solution decomposes at high temperature and lithium source, source of iron, manganese source, P source compound are before electrostatic spinning Other side reactions occur, electrostatic spinning temperature should be controlled at 70 DEG C or less.Pore creating material type in the prior art is more, including carbon Sour hydrogen ammonium, urea, starch, PMMA, PVP, PVA etc..But the fusing point of these pore creating materials is higher, at 100 DEG C or more.Therefore in step It is rapid 1) in, pore creating material be low melting point organic matter, be selected from least one of ethylene carbonate (EC), polyethylene glycol (PEG).Wherein The relative molecular mass of polyethylene glycol is 200~20000, and fusing point changes with the degree of polymerization or the difference of average molecular weight. Such as the polyethylene glycol for being 400 for relative molecular mass, fusing point are 4~8 DEG C, the polyethylene glycol that relative molecular mass is 600, Fusing point is 20~25 DEG C, the polyethylene glycol that relative molecular mass is 6000, and fusing point is 56~63 DEG C.Ethylene carbonate is not related to list Body number, fusing point are 35~38 DEG C.Above-mentioned pore creating material can satisfy at a temperature of the electrostatic spinning of the application, and pore creating material is liquid Requirement.
A kind of improvement of preparation method as the application lithium ferric manganese phosphate positive electrode, in step 3), spinning solution In Li source compound, Fe source compound, manganese source compound, P source compound dosage by lithium, iron, manganese, P elements substance The ratio of amount be calculated as 1:0.2~0.8:0.2~0.8:1.In embodiments herein, the ratio of the amount of above-mentioned substance is preferably 1: 0.2:0.8:1、1:0.3:0.7:1、1:0.4:0.6:1、1:0.5:0.5:1、1:0.6:0.4:1、1:0.7:0.3:1、1:0.8: 0.2:1.The mass content of high molecular polymer in spinning solution accounts for the 1-25% of spinning solution gross mass.
A kind of improvement of preparation method as the application lithium ferric manganese phosphate positive electrode, in step 3), spinning solution The mass content of middle pore creating material accounts for the 1%-10% of spinning solution gross mass, preferably 1%-5%.The mass content mistake of pore creating material Low, the quantity and density in the obtained hole in lithium ferric manganese phosphate nanofiber are too small, the improvement to lithium ion battery high rate performance It is unobvious.The mass content of pore creating material is excessively high, and the quantity and density in the obtained hole in lithium ferric manganese phosphate nanofiber are excessive, receives Fiber is excessively loose is easily broken off for rice, also results in the decline of battery high rate performance.Compared with single pore creating material, mixing pore-creating is used Agent can obtain better chemical property, preferably the ratio between amount of substance of ethylene carbonate and polyethylene oxide be 1~3:1~ 3.When the ratio between amount of substance of the two is 2:1, the performance of battery is best.
A kind of improvement of preparation method as the application lithium ferric manganese phosphate positive electrode, in step 4), electrostatic spinning The structural schematic diagram of device as shown in Figure 1: injects spinning solution 1 in the injection needle 2 of electrospinning device, passes through high-voltage electricity Source 4 generates strong electrical field between injection needle 2 and receiver board 3.Controlling electrostatic spinning temperature is 5-60 DEG C, preferably 30-60 DEG C, electric Pressure is 5-60KV, and solidification distance is 10-35cm, and the solvent in spinning solution 1, which volatilizees, at this time solidifies, and pore creating material still keeps liquid Body state is sprayed from the tip of injection needle 2, obtains nano-porous fiber.
A kind of improvement of preparation method as the application lithium ferric manganese phosphate positive electrode, by nanometer obtained in step 4) It is sintered after porous fibre vacuum drying, makes high molecular polymer cracking carbonization, form the ferric phosphate of porous nano-fibre shape Manganese lithium anode material.In step 5), sintering carry out under anaerobic, atmosphere be nitrogen, argon gas, hydrogen it is one or more Gaseous mixture, sintering temperature are 500-750 DEG C, and sintering time is 5-14 hours, furnace cooling later.Preferably sintering temperature is 600-700 DEG C, the uniform lithium ferric manganese phosphate of available component.
The application further relates to a kind of lithium ion battery, containing positive plate, negative electrode tab, isolation film and electrolyte, just The lithium ferric manganese phosphate positive electrode of the application is used in pole piece.
Contain electrolyte, organic solvent and additive in electrolyte, in which:
Electrolyte be selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, LiN(SO2Rf)2、LiN(SO2F)(SO2Rf), double trifluoromethanesulfonimide lithiums, bis- (fluorine sulphonyl) imine lithiums, double oxalic acid boric acid At least one of lithium, difluorine oxalic acid boracic acid lithium, wherein Rf=-CnF2n+1, n be 1~10 integer, preferably lithium hexafluoro phosphate or LiN(SO2Rf)2。
Organic solvent is selected from carbonic ester, carboxylate, sulfuric ester, sulfone class, nitrile compounds etc., and carbonic ester is selected from cyclic carbonate Ester, linear carbonate；Carboxylate is selected from cyclic carboxylic esters, chain carboxylate；Sulfuric ester is selected from cyclic sulfates, chain sulfuric ester Deng.It specifically can be selected from following organic solvent to be not limited to this: ethylene carbonate, propylene carbonate, dimethyl carbonate, carbonic acid diethyl Ester, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, acetic acid second Ester, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N- methylacetamide, acetonitrile, at least two in methyl sulfide.
Embodiment 1
The preparation of lithium ferric manganese phosphate positive electrode P1~P18
In a solvent by high molecular polymer and pore creating material dissolution, then according to molar ratio n (Li): n (Fe): n (Mn): n (P) ferrous acetate (Fe (CH is added in=1:0.5:0.5:13COO)2), four hydration manganese acetate (Mn (CH3COO)2·4H2) and phosphoric acid O Dihydro lithium (LiH2PO4), obtained spinning solution is injected in electrostatic spinning apparatus syringe after being uniformly dispersed, control spinning electricity Pressure and solidification distance carry out electrostatic spinning.After obtained electrostatic spinning product is dried in vacuo, carry out in a nitrogen atmosphere Sintering, obtains lithium ferric manganese phosphate positive electrode LiFe0.5Mn0.5PO4, design parameter is as described in Table 1.
Table 1
Fig. 2 is the scanning electron microscope (SEM) photograph of positive electrode P2, it can be seen that the material is elongated filiform, and width is nanometer Grade.Since amplification factor is limited, pore structure can not be seen in electron microscope, structural schematic diagram is as shown in figure 3, on the surface of the material With internal distribution hole structure.
Comparative example 1
Lithium ferric manganese phosphate positive electrode is prepared according to the method for embodiment 1, and difference is, material rate and preparation parameter are such as Shown in table 2:
Table 2
Wherein, the substance is not added for "-" expression.
For the porous nano-fibre shape lithium ferric manganese phosphate prepared using embodiment 1 and comparative example 1 as positive electrode, acetylene black is to lead Electric agent, polytetrafluoroethylene (PTFE) are binder, and N-Methyl pyrrolidone is solvent, by quality proportioning lithium ferric manganese phosphate: binder: conductive Anode electrode piece is made in agent=90:5:5.Using lithium metal as cathode electrode slice.By quality proportioning ethylene carbonate: dimethyl carbonic acid Ester=4:6 prepares electrolyte, wherein lithium hexafluoro phosphate 1.0mol/L.By anode electrode piece, negative electricity pole piece, electrolyte, poly- second Alkene isolation film is assembled together as button half-cell.
Using the resulting lithium ferric manganese phosphate of embodiment 1 as the lithium ion battery of positive electrode be denoted as respectively battery C1~ C18, wherein positive electrode P1 corresponds to battery C1, and positive electrode P2 corresponds to battery C2, and so on.It is resulting using comparative example 1 Lithium ferric manganese phosphate is denoted as battery DC1~DC7 as the lithium ion battery of positive electrode respectively.
Experimental example
Testing example 1 and comparative example 1 prepare the charge-discharge performance and high rate performance of battery, and detection method is as follows:
Battery charging/discharging performance testing, it carries out in accordance with the following steps:
A) battery with 0.1C (1C=0.38mA) electric current constant-current charge to 4.5V when, turn constant-voltage charge, until charging current drops Stop charging when to 0.05C multiplying power electric current；
B) battery with 0.1C multiplying power electric current constant-current discharge to 2.8V when stop electric discharge；
C) charge/discharge capacity of battery is counted.
The test of battery high rate performance, the first discharge specific capacity of 1C/2C/3C/5C multiplying power is tested respectively, is with 3C multiplying power Example carries out in accordance with the following steps:
A) battery with 3C multiplying power electric current constant-current charge to 4.5V when, turn constant-voltage charge, until charging current is down to 0.05C multiplying power Stop charging when electric current；
B) battery with 3C multiplying power electric current constant-current discharge to 2.8V when stop electric discharge；
C) percentage of battery discharge capacity and charging capacity for the first time is calculated.
The charge-discharge performance test result of battery C2 is shown in Fig. 4, reversible capability of charging and discharging 162.1mAh/ in embodiment 1 g.Battery high rate performance test result is shown in Fig. 5, the first discharge specific capacity of 1C/2C/3C/5C is respectively 144.3,133.8, 129.4、120.5mAh/g。
The specific testing result of 1 battery of embodiment 1 and comparative example is as shown in table 3:
Table 3
In conjunction with table 1-3 content it is found that will cause the number cells in nanofiber as Content of Pore-forming Agents excessively high (> 10%) Amount is excessive, causes positive electrode broken or fracture, and battery performance decline is advisable with Content of Pore-forming Agents 1%~5%.
If spinning temperature is too low (35 DEG C of <), pore creating material is unable to reach fusing point and plays a role, and can not form porous fibre.Temperature Spend high pore creating material and high molecular polymer it is volatile and denaturation, equally cannot get nanofiber of good performance.Electrostatic spinning Temperature is advisable at 35~60 DEG C.
Sintering temperature excessively high (700 DEG C of >) leads to nanofiber embrittlement, and temperature is too low to cause material crystalline bad, can not shape At the lithium ferric manganese phosphate crystal of well-crystallized.Relative to sintering time, sintering temperature is even more important.
Therefore, the important parameter for determining that lithium ferric manganese phosphate nanofiber is formed includes Content of Pore-forming Agents, spinning temperature and burning Junction temperature.Low melting point pore creating material is such as selected, influence of the type to product property is less big.
Embodiment 2
The preparation of lithium ferric manganese phosphate positive electrode P19~P20
Lithium ferric manganese phosphate positive electrode is prepared according to the method for P2 in embodiment 1, difference is, changes electrostatic spinning temperature Degree, source of iron, manganese source, phosphorus source and lithium source type and the mass ratio of the material example and sintering temperature and time, design parameter such as 3 institute of table Show:
Table 3
Wherein, that P19 is obtained is the LiFe of porous nano-fibre shape0.4Mn0.6PO4, what P20 was obtained is porous nano-fibre The LiFe of shape0.2Mn0.8PO4, the test result for being assembled into battery is similar to Example 1.
Embodiment 3
The preparation of lithium ferric manganese phosphate positive electrode P21~P25
Prepare lithium ferric manganese phosphate positive electrode according to the method for P2 in embodiment 1, difference is, using mixing pore creating material, Wherein design parameter such as 4 institute of table of the type (wherein the molecular weight of polyethylene glycol is 6000) and the mass ratio of the material example of pore creating material Show:
Table 4
Above-mentioned lithium ferric manganese phosphate positive electrode P21~P25 is assembled into battery according to the method for embodiment 1, obtains battery C21 ~C25.According to the charge-discharge performance and high rate performance of the method test battery of experimental example, the results are shown in Table 5.
Table 5
As known from Table 5, using mixing pore creating material, obtained positive electrode has better chemical property, especially works as carbon When the ratio between amount of substance of vinyl acetate and polyethylene oxide is 2:1, battery performance is optimal.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application Protection scope should be subject to the range that the claim of this application is defined.

Claims (11)

1. a kind of lithium ferric manganese phosphate positive electrode, chemical formula LiFe1-xMnxPO4, 0 < x < 1, which is characterized in that use electrostatic Spin processes are prepared, and electrostatic spinning temperature is 35-60 DEG C in the method for electrostatic spinning, the lithium ferric manganese phosphate positive electrode For nanofiber, the diameter of the nanofiber is 0.1-0.5 μm, surface and internal distribution hole.
2. the preparation method of lithium ferric manganese phosphate positive electrode as described in claim 1, which comprises the following steps:
1) Li source compound, Fe source compound, manganese source compound and P source compound are dissolved in the first solvent, obtain forerunner Liquid solution；
2) high molecular polymer and pore creating material are dissolved in the second solvent, obtain polymer solution；
3) precursor solution is mixed with the polymer solution, obtains spinning solution；
4) electrostatic spinning is carried out to the spinning solution, obtains lithium ferric manganese phosphate presoma, electrostatic spinning temperature is 35-60 DEG C；
5) the lithium ferric manganese phosphate presoma is sintered, obtains the lithium ferric manganese phosphate positive electrode.
3. according to the method described in claim 2, it is characterized in that, the Fe source compound is selected from step 1) and step 2) One of ferric oxalate, ferrous oxalate, ferric nitrate, iron ammonium sulfate, iron chloride, frerrous chloride, ferrous acetate are a variety of；
The manganese source compound is selected from one of manganese acetate, manganese nitrate, ammonium manganous sulfate, manganese carbonate, manganese oxalate or a variety of；
Phosphorus source compound is selected from one hydrogen lithium of phosphoric acid, lithium dihydrogen phosphate, monoammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, phosphoric acid One of hydrogen diammonium is a variety of；
The Li source compound is in lithium carbonate, lithium hydroxide, lithium nitrate, one hydrogen lithium of phosphoric acid, lithium dihydrogen phosphate, lithium acetate It is one or more；
The high molecular polymer is selected from polyvinyl formal, polyethylene glycol oxide, polyacrylonitrile, Kynoar, polyethylene One of pyrrolidones, polymethyl methacrylate are a variety of；
First solvent and the second solvent are volatile organic solvent, are selected from ethyl alcohol, acetone, chloroform, methylene chloride, N, N- One of dimethylformamide, N-Methyl pyrrolidone are a variety of.
4. according to the method described in claim 2, it is characterized in that, the pore creating material is selected from ethylene carbonate, gathers in step 2) At least one of ethylene glycol.
5. according to the method described in claim 2, it is characterized in that, in step 3), Li source compound in the spinning solution, Fe source compound, manganese source compound, P source compound dosage be calculated as 1 by the ratio of amount of substance of lithium, iron, manganese, P elements: 0.2~0.8:0.2~0.8:1, the mass content of high molecular polymer account for the 1-25% of spinning solution gross mass.
6. according to the method described in claim 2, it is characterized in that, in step 3), the quality of pore creating material in the spinning solution Content accounts for the 1%-10% of spinning solution gross mass.
7. according to the method described in claim 6, it is characterized in that, in step 3), the quality of pore creating material in the spinning solution Content accounts for the 1%-5% of spinning solution gross mass.
8. according to the method described in claim 2, it is characterized in that, in step 4), electrostatic spinning voltage is 5-60KV, solidification away from From for 10-35cm.
9. according to the method described in claim 2, it is characterized in that, sintering atmosphere is nitrogen, argon gas, hydrogen in step 5) One or more gaseous mixtures, sintering temperature are 500-750 DEG C, and sintering time is 5-14 hours.
10. according to the method described in claim 9, it is characterized in that, sintering temperature is 600-700 DEG C in step 5).
11. a kind of lithium ion battery, which is characterized in that it uses any in described in claim 1 or claim 2 to 10 The lithium ferric manganese phosphate positive electrode that item the method is prepared.
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