CN104577113B - A kind of graphene coated lithium ferric manganese phosphate positive electrode and preparation method thereof - Google Patents
A kind of graphene coated lithium ferric manganese phosphate positive electrode and preparation method thereof Download PDFInfo
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- CN104577113B CN104577113B CN201410788444.6A CN201410788444A CN104577113B CN 104577113 B CN104577113 B CN 104577113B CN 201410788444 A CN201410788444 A CN 201410788444A CN 104577113 B CN104577113 B CN 104577113B
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of graphene coated lithium ferric manganese phosphate positive electrode and preparation method thereof, the formula of described graphene coated lithium ferric manganese phosphate positive electrode is：LiFexMn1‑xPO4/ graphene, first by homemade MnPO4·H2O、FePO4·2H2O nano powders are well mixed by certain mol proportion mechanical lapping, then mixed powder is added in the uniform graphene oxide dispersion solvent of ultrasonic disperse, lithium metal solution is gradually added under the conditions of magnetic agitation to be reduced, reaction adds a certain amount of lithium complexing agent after terminating, stir, filter, wash after obtain presoma, 600~800 DEG C of 4~10h of high-temperature process in inert atmosphere, that is, obtain the LiFe of graphene coatedxMn1‑xPO4.The graphene coated lithium ferric manganese phosphate positive electrode of the present invention has the superior chemical properties such as high voltage, high power capacity, high circulation stability.
Description
Technical field
The invention belongs to field of lithium ion battery material, it is related to a kind of anode material for lithium-ion batteries and preparation method thereof,
More particularly to a kind of graphene coated lithium ferric manganese phosphate positive electrode and preparation method thereof.
Background technology
With the developing of epoch, the progress of science and technology, the application field of lithium ion battery constantly extends, gradually in daily life
In play key player.With the arriving in electric automobile epoch, the research boom of lithium ion battery has even more been started.Often at present
Anode material for lithium-ion batteries LiCoO2、LiNiO2And LiMn2O4Electric automobile can not all be met to many of electrokinetic cell
It is required that.LiFePO4Positive electrode has not only concentrated the advantage of above-mentioned three kinds of positive electrodes：Price is low, Stability Analysis of Structures and security
It is good, and LiFePO4Long circulation life, good properties at high temperature and high-rate discharge ability be even more to have attracted power battery material
The concern of researcher.Although LiFePO4There are the above, but LiFePO4Low (the 3.4V vs of positive electrode voltage platform
Li+/ Li), energy density hardly possible, which is improved, becomes the bottleneck of application.
Belong to the LiMnPO of rhombic system4With LiFePO4There are identical olivine structural and close theoretical capacity
(171mAh/g) etc. many and LiFePO4The similar advantage of material, and LiMnPO4Voltage platform (4.1V vs Li+/Li)
Apparently higher than LiFePO4Material, but LiMnPO4Conductance compare LiFePO4It is lower, or even only LiFePO4Thousand/
One.And lithium ferric manganese phosphate is with LiMnPO4And LiFePO4Solid solution thereof exist, the performance of above two material can be made to make the best use of the advantages and kept away
It is short, but the olivine structural of the lithium ferric manganese phosphate of prior art synthesis, still cause the electronic conductivity and ionic conductance of material
Rate is relatively low.
The content of the invention
The present invention for the electronic conductivity of lithium ferric manganese phosphate positive electrode and the problem of relatively low ionic conductivity there is provided
A kind of graphene coated lithium ferric manganese phosphate positive electrode and preparation method thereof.
A kind of graphene coated lithium ferric manganese phosphate positive electrode, described graphene coated lithium ferric manganese phosphate positive electrode
Formula is：LiFexMn1-xPO4/ graphene, is prepared by following steps：
Step 1：First manganese source and phosphorus source are dissolved in deionized water respectively, and oxidant is added in manganese source solution；Secondly,
According to element ratio n (Mn)：N (P)=1:1 measures manganese source solution and phosphorus source solution, is mixed evenly and obtains manganese source and phosphorus source
Mixed solution, adds dispersion liquid, and the volume of the dispersion liquid is identical with the volume of manganese source and phosphorus source mixed solution；Then in water
Stirring generation sediment in bath；MnPO will be obtained after sediment suction filtration, washing and drying4·H2O nano powders；Wherein bath temperature
For 30~60 DEG C, 1~4h of mixing time；
Step 2：Source of iron and phosphorus source are dissolved in deionized water respectively, when source of iron is ferrous iron, added in source of iron solution
Oxidant；According to element ratio n (Fe)：N (P)=1:1 measures under source of iron solution and phosphorus source solution, stirring condition, and phosphorus source is molten
Liquid, which is gradually dropped in source of iron solution, obtains source of iron and phosphorus source mixed solution, adds dispersion liquid, the volume and iron of the dispersion liquid
Source is identical with the volume of phosphorus source mixed solution；Then sediment is generated in stirred in water bath；By sediment suction filtration, washing and drying
After obtain FePO4·2H2O nano powders；Wherein bath temperature is 30~60 DEG C, 1~4h of mixing time；
Step 3：Lithium metal is added in nonaqueous solvents and dissolved, 1~15mol/L lithium solution is formed, sealed stand-by；
Step 4：Add graphene oxide into dispersion solvent, formed at 0.01~0.05g/mL suspension, ultrasound
2~4h is managed, graphene oxide dispersion is obtained, wherein supersonic frequency is 30~60KHz；
Step 5：By MnPO described in step 14·H2FePO described in O and step 24·2H2Two kinds of nano powders of O press n (Fe)：n
(Mn) mol ratio=0.25~4.0 is placed in ball grinder, is added decentralized medium, preferably just submerging powder, is used ball milling
Machine ball milling is mixed evenly, and is dried to obtain mixed powder, wherein 2~6h of Ball-milling Time, 110~130 DEG C of drying temperature, drying time
4~8h；
Step 6：Step 5 mixed powder is added in the graphene oxide dispersion in step 4 carry out it is ultrasonically treated extremely
It is uniformly dispersed, obtains mixed system, the numerical value of the quality of graphene oxide is mixed powder wherein in graphene oxide dispersion
0.1 (x+78)~0.3 (x+78) of integral molar quantity numerical value times, 3~6h of sonication treatment time, supersonic frequency is 30~60KHz；
Step 7：Lithium solution described in step 3 is gradually dropped in the finely dispersed mixed system of step 6 under stirring condition, stirred
Mix complete to reaction, the mole that wherein lithium GOLD FROM PLATING SOLUTION belongs to lithium is 1~1.5 of the integral molar quantity of mixed powder described in step 5
Times；
Step 8：Under stirring condition, addition lithium complexing agent in complete mixed system is reacted to step 7,0.5~2h is stirred
Make complexing completely, filtering, washing obtain presoma, wherein the amount of lithium complexing agent is the lithium GOLD FROM PLATING SOLUTION added in the step 7
Belong to 1~1.3 times of lithium mole；
Step 9：Presoma described in step 8 is dried in vacuo, then grinds uniform into powder, powder is then loaded into corundum boat
It is interior, cool to room temperature with the furnace after sintering in an inert atmosphere, obtain graphene coated lithium ferric manganese phosphate positive electrode, wherein vacuum
Drying temperature is 60~90 DEG C, 10~24h of drying time, 600~800 DEG C of sintering temperature, 4~10h of sintering time；
Wherein, the manganese source is that manganese acetate, manganese oxalate, formic acid manganese, manganese sulfate, manganese nitrate and manganese chloride solubility contain manganese
At least one of compound, preferably manganese nitrate；
Phosphorus source is phosphoric acid, ammonium phosphate, Diammonium phosphate (DAP), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, biphosphate
At least one of soluble phosphorus-containing compound of potassium, dipotassium hydrogen phosphate, sodium phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate, preferably
Phosphoric acid and sodium phosphate；
The source of iron is iron chloride, ferric sulfate, ferric nitrate, frerrous chloride, ferrous sulfate, ferrous nitrate, ferrous oxalate, vinegar
At least one of sour soluble iron containing compoundses of ferrous, ferrous bromide, ferric nitrate preferably；
The oxidant is H2O2、Na2O2, nitric acid, the concentrated sulfuric acid, at least one of HClO and NaClO, dioxygen preferably
Water；
The dispersion liquid is absolute ethyl alcohol, acetone, ethylene glycol, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methylpent
At least one of alcohol, cellulose derivative, polyacrylamide, guar gum and fatty acid polyethylene glycol ester；
The lithium metal is at least one of metallic lithium powder, metal lithium sheet, block lithium and lithium silk；
The nonaqueous solvents is in liquefied ammonia, glycol dimethyl ether, tetrahydrofuran, ether, methyl ether or dimethyl acetamide
At least one, preferably liquefied ammonia；
The dispersion solvent is at least one of methyl ether, ether or acetone；
The graphene oxide is to be aoxidized made from one of Brodie methods, Staudenmaier methods and Hummers methods
Graphene, preferably Hummers methods；
The decentralized medium is at least one of ethanol, ethylene glycol and acetone, preferred alcohol；
The complexing agent is at least one of expoxy propane, acetonitrile, 12-crown-4 and dimethyl sulfoxide (DMSO), preferably epoxy third
Alkane；
The inert atmosphere is at least one of helium, argon gas or nitrogen；
The scope of the x is 0.2≤x≤0.8.Allotment MnPO is carried out in this scope4·H2O and FePO4·2H2O nano powders
Consumption, the graphene coated lithium ferric manganese phosphate positive electrode of preparation is used for having preferable discharge platform and energy close in battery
Degree.
The present invention prepares graphene coated lithium ferric manganese phosphate positive electrode using reaction in-situ, in synthesis LiFexMn1-xPO4
While material, in LiFexMn1-xPO4Graphene conductive network of the material surface in-situ preparation cladding with excellent conductive performance
Film, not only substantially increases the electric conductivity of material, but also reduces electrolyte to Mn in material2+Erosion dissolving, improve electricity
Pond cycle performance；The graphene conductive network film of material surface cladding can also suppress the growth of material crystals particle, improve material
Ion diffusivity；Show through electrochemical property test, graphene coated lithium ferric manganese phosphate positive electrode tool prepared by this programme
There are the superior chemical properties such as high working voltage, high power capacity, high circulation stability.
This programme selects MnPO4·H2O and FePO4·2H2O nano powders are homemade raw material, are preparing LiFexMn1-xPO4
The proportioning of middle ferrimanganic element can be adjusted freely, and the discharge platform and battery energy density of battery material within the specific limits may be used
Regulation and control.
Lithium metal solution therein is also used in addition to providing lithium source for materials synthesis as reducing agent；In the present invention
Lithium metal is by Mn3+、Fe3+Quantitative reduction is Mn2+、Fe2+While, graphene oxide is also reduced to graphene, completed to phosphoric acid
Ferric manganese phosphate anode material carries out graphene coated in situ.This scheme preparation method is simple, and the simple equipments used are easy to operate, is adapted to
Large-scale industrial production.
As a further improvement on the present invention, MnPO described in step 54·H2FePO described in O and step 24·2H2Two kinds of O receives
The mol ratio of ground rice is n (Fe)：N (Mn)=0.5~3.0, more preferably n (Fe)：N (Mn)=4:6、5:5、6:4.More excellent n
(Fe)：N (Mn) ratio causes the graphene coated lithium ferric manganese phosphate positive electrode prepared to have good chemical property.
As a further improvement on the present invention, the quality of graphene oxide in graphene oxide dispersion described in step 6
Numerical value is 0.15 (x+78)~0.2 (x+78) times of the mixed powder integral molar quantity numerical value.Using the graphene oxide of optimization
Amount can reach to the preferable covered effect of lithium ferric manganese phosphate positive electrode, while improve lithium ferric manganese phosphate positive electrode conduction
Property.
As a further improvement on the present invention, lithium GOLD FROM PLATING SOLUTION described in step 7 belongs to the mole of lithium to mix described in step 5
1.1~1.3 times of the integral molar quantity of powder.Using the mole of the lithium metal more slightly larger than the integral molar quantity of the mixed powder,
Ensure Mn3+、Fe3+Quantitative reduction is Mn2+、Fe2+While graphene oxide is also reduced to graphene, while for material close
Into proper amount of lithium source is provided, it is unlikely to the excessive lithium of introducing again and causes other side effects.
As a further improvement on the present invention, the amount of lithium complexing agent described in step 8 is the lithium solution that adds in the step 7
1~1.2 times of middle lithium metal mole, more preferably 1~1.1 times.Using appropriate complexing agent, it is no less than metallic lithium atoms
Amount, it is ensured that the metallic lithium atoms added in scheme can be complexed agent protection, without regard to the other impurity of introducing.
As a further improvement on the present invention, the mole specific concentration of lithium solution described in step 3 is 1~10mol/L, more preferably
1~5mol/L.
As a further improvement on the present invention, the bath temperature described in step 1 and step 2 is 40~50 DEG C, during stirring
Between 2~3h；Suitable bath temperature and time are conducive to controlling reaction speed, and the small nano powder of particle diameter is made.
2~3h of sonication treatment time described in step 4,2~4h of sonication treatment time described in step 6, step 4 and step 6 institute
Supersonic frequency is stated for 40~50KHz；3~5h of Ball-milling Time described in step 5, the ball mill is planetary ball mill, described dry
Dry 110~120 DEG C of temperature, the 3~6h of drying time；The mode of stirring condition described in step 7 and step 8 is magnetic agitation,
Speed of agitator is 100~400r/min.
Vacuum drying temperature described in step 9 is 70~80 DEG C, 12~20h of drying time, and 600~800 DEG C of sintering temperature is burnt
3~8h of knot time；More preferably vacuum drying temperature is 80 DEG C, and drying time is 10h；More preferably sintering temperature is 760 DEG C, sintering
Time is 8h；Using the technological parameter described in vacuum drying and the technical program, it can be prevented while realization is completely dried
The oxidation of lithium metal, it is to avoid introduce new material.
Present invention also offers a kind of preparation method of graphene coated lithium ferric manganese phosphate positive electrode, following step is included
Suddenly：
Step 1：First manganese source and phosphorus source are dissolved in deionized water respectively, and oxidant is added in manganese source solution；Secondly,
According to element ratio n (Mn)：N (P)=1:1 measures manganese source solution and phosphorus source solution, is mixed evenly and obtains manganese source and phosphorus source
Mixed solution, adds dispersion liquid, and the volume of the dispersion liquid is identical with the volume of manganese source and phosphorus source mixed solution；Then in water
Stirring generation sediment in bath；MnPO will be obtained after sediment suction filtration, washing and drying4·H2O nano powders；Wherein bath temperature
For 30~60 DEG C, 1~4h of mixing time；
Step 2：Source of iron and phosphorus source are dissolved in deionized water respectively, when source of iron is ferrous iron, added in source of iron solution
Oxidant；According to element ratio n (Fe)：N (P)=1:1 measures under source of iron solution and phosphorus source solution, stirring condition, and phosphorus source is molten
Liquid, which is gradually dropped in source of iron solution, obtains source of iron and phosphorus source mixed solution, adds dispersion liquid, the volume and iron of the dispersion liquid
Source is identical with the volume of phosphorus source mixed solution；Then sediment is generated in stirred in water bath；By sediment suction filtration, washing and drying
After obtain FePO4·2H2O nano powders；Wherein bath temperature is 30~60 DEG C, 1~4h of mixing time；
Step 3：Lithium metal is added in nonaqueous solvents and dissolved, 1~15mol/L lithium solution is formed, sealed stand-by；
Step 4：Add graphene oxide into dispersion solvent, formed at 0.01~0.05g/mL suspension, ultrasound
2~4h is managed, graphene oxide dispersion is obtained, wherein supersonic frequency is 30~60KHz；
Step 5：By MnPO described in step 14·H2FePO described in O and step 24·2H2Two kinds of nano powders of O press n (Fe)：n
(Mn) mol ratio=0.25~4.0 is placed in ball grinder, is added decentralized medium, preferably just submerging powder, is used ball milling
Machine ball milling is mixed evenly, and is dried to obtain mixed powder, wherein 2~6h of Ball-milling Time, 110~130 DEG C of drying temperature, drying time
4~8h；
Step 6：Step 5 mixed powder is added in the graphene oxide dispersion in step 4 carry out it is ultrasonically treated extremely
It is uniformly dispersed, obtains mixed system, the numerical value of the quality of graphene oxide is mixed powder wherein in graphene oxide dispersion
0.1 (x+78)~0.3 (x+78) of integral molar quantity numerical value times, 3~6h of sonication treatment time, supersonic frequency is 30~60KHz；
Step 7：Lithium solution described in step 3 is gradually dropped in the finely dispersed mixed system of step 6 under stirring condition, stirred
Mix complete to reaction, the mole that wherein lithium GOLD FROM PLATING SOLUTION belongs to lithium is 1~1.5 of the integral molar quantity of mixed powder described in step 5
Times；
Step 8：Under stirring condition, addition lithium complexing agent in complete mixed system is reacted to step 7,0.5~2h is stirred
Make complexing completely, filtering, washing obtain presoma, wherein the amount of lithium complexing agent is the lithium GOLD FROM PLATING SOLUTION added in the step 7
Belong to 1~1.3 times of lithium mole；
Step 9：Presoma described in step 8 is dried in vacuo, then grinds uniform into powder, powder is then loaded into corundum boat
It is interior, cool to room temperature with the furnace after sintering in an inert atmosphere, obtain graphene coated lithium ferric manganese phosphate positive electrode, wherein vacuum
Drying temperature is 60~90 DEG C, 10~24h of drying time, 600~800 DEG C of sintering temperature, 4~10h of sintering time；
Wherein, the manganese source is that manganese acetate, manganese oxalate, formic acid manganese, manganese sulfate, manganese nitrate and manganese chloride solubility contain manganese
At least one of compound；
Phosphorus source is phosphoric acid, ammonium phosphate, Diammonium phosphate (DAP), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, biphosphate
At least one of soluble phosphorus-containing compound of potassium, dipotassium hydrogen phosphate, sodium phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate；
The source of iron is iron chloride, ferric sulfate, ferric nitrate, frerrous chloride, ferrous sulfate, ferrous nitrate, ferrous oxalate, vinegar
At least one of sour soluble iron containing compoundses of ferrous, ferrous bromide；
The oxidant is H2O2、Na2O2, nitric acid, the concentrated sulfuric acid, at least one of HClO and NaClO；
The dispersion liquid is absolute ethyl alcohol, acetone, ethylene glycol, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methylpent
At least one of alcohol, cellulose derivative, polyacrylamide, guar gum and fatty acid polyethylene glycol ester；
The lithium metal is at least one of metallic lithium powder, metal lithium sheet, block lithium and lithium silk；
The nonaqueous solvents is in liquefied ammonia, glycol dimethyl ether, tetrahydrofuran, ether, methyl ether or dimethyl acetamide
It is at least one；
The dispersion solvent is at least one of methyl ether, ether or acetone；
The graphene oxide is to be aoxidized made from one of Brodie methods, Staudenmaier methods and Hummers methods
Graphene；
The decentralized medium is at least one of ethanol, ethylene glycol and acetone；
The complexing agent is at least one of expoxy propane, acetonitrile, 12-crown-4 and dimethyl sulfoxide (DMSO)；
The inert atmosphere is at least one of helium, argon gas or nitrogen.
The invention provides the technology that a kind of in-stiu coating graphene improves lithium ferric manganese phosphate positive electrode electrical conductivity, scheme
In be respectively synthesized MnPO first4·H2O and FePO4·2H2O nano powders, it is then with certain proportion that above two nano powder is mechanical
Ball milling is mixed, and is added in the uniform graphene oxide dispersion solvent of advance ultrasonic disperse, under the conditions of magnetic agitation, is gradually added
The lithium metal solution for entering the certain mol proportion prepared is reduced, and reaction adds a certain amount of lithium complexing agent after terminating, and stirs
Presoma is obtained after mixing uniform, filtering, washing, 600~800 DEG C of 4~10h of high-temperature process, that is, obtain stone in inert atmosphere
The LiFe of black alkene claddingxMn1-xPO4.Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention selects homemade MnPO4·H2O and FePO4·2H2O nano powders are being prepared as raw material
LiFexMn1-xPO4The proportioning of middle ferrimanganic element can be adjusted freely, so close to the discharge platform and the energy content of battery of battery material
Spend controllable within the specific limits.
(2) present invention is in LiFexMn1-xPO4Graphene conductive network film of the material surface cladding with excellent conductive performance,
The electric conductivity of material is not only substantially increased, but also reduces electrolyte to Mn in material2+Erosion dissolving, improve material
Charging and discharging capacity and cycle performance；The graphene conductive network film of material surface cladding can suppress the life of material crystals particle
It is long, the ion diffusivity of material is improved, the first charge-discharge efficiency of material is improved.
(3) lithium metal solution in addition to providing lithium source for materials synthesis, is also used, in this hair as reducing agent in the present invention
Bright middle lithium metal is by Mn3+、Fe3+Quantitative reduction is Mn2+、Fe2+While, graphene oxide is also reduced to graphene, completed
Graphene coated in situ is carried out to lithium ferric manganese phosphate positive electrode.This scheme preparation method, the equipment used are simple and easy to operate,
It is adapted to large-scale industrial production.
(4) the lithium ferric manganese phosphate positive electrode for the graphene coated that the present invention is synthesized does not only have higher operating voltage, and
And with higher specific capacity so that battery energy density is improved significantly.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.
Embodiment 1：
Weigh 125.5045g Mn (NO3)2·4H2O is dissolved in 200ml deionized waters, pipettes 29.10ml H3PO4(density
For 1.685g/ml) it is added in manganese nitrate solution, 200ml ethanol is then added, 3h is stirred vigorously in 45 DEG C of water-baths, there is light
Green precipitate is generated.Gained is precipitated into suction filtration, then washed with deionized water, ethanol 3 times, 80 DEG C of drying both obtain MnPO4·H2O
Nano powder.
Weigh 201.9985g Fe (NO3)3·9H2O is dissolved in 300ml deionized waters, weighs 74.5435g (NH4)3PO4It is molten
In 100ml deionized waters, two kinds of solution are mixed in 1000ml beaker, 400ml ethanol, 45 DEG C of water-baths is then added
In be stirred vigorously 3h, have white precipitate generation.Gained is precipitated into suction filtration, then washed with deionized water, ethanol 3 times, 80 DEG C of bakings
It is dry, both obtain FePO4·2H2O nano powders.
10.50g metal lithium sheet is added gradually to fill in the Dewar bottle of 300mL liquefied ammonia and dissolved, form 5mol/L's
Blue lithium metal solution, is sealed stand-by.
The graphene oxide for taking 3.4936g Hummers methods to prepare is added in 200mL acetone, in 40KHz supersonic frequency
Ultrasonically treated 2h under rate, is made graphene oxide dispersion.
By n (Fe)：N (Mn)=4:6 molar ratios weigh 14.9478g FePO respectively4·2H2O、20.1510g
MnPO4·H2Two kinds of nano powders of O are placed in ball grinder, add ethanol decentralized medium, preferably just not having powder, using planetary
Ball mill ball milling 4h is mixed evenly, 120 DEG C of dry 6h..Above-mentioned scattered graphene oxide is added to after grinding is uniform to disperse
In liquid, continue ultrasonically treated 3h under 40KHz supersonic frequency to being uniformly dispersed.50mL 5mol/L lithium metal solution is taken,
Gradually it is added drop-wise under conditions of magnetic agitation in above-mentioned finely dispersed mixed system.After fully reacting, then it is gradually added into
11.62g expoxy propane, stirring 1h makes complexing completely, and suction filtration, absolute ethyl alcohol wash to obtain presoma.By presoma in 80 DEG C of vacuum
Under the conditions of dry 10h.Grind uniform after drying, then load powder in corundum boat, it is high at a temperature of 760 DEG C in nitrogen
Temperature sintering 8h.Furnace cooling produces the LiFe of graphene coated to room temperature0.4Mn0.6PO4, the covering amount of graphene is 10wt%.
Electrochemical property test：By the LiFe of above-mentioned graphene coated0.4Mn0.6PO4, binding agent (PVDF) and conductive agent second
Acetylene black presses 75:10:15 ratio is sufficiently mixed uniformly in solvent (1-METHYLPYRROLIDONE), and gained slurry is applied into aluminium foil
On, 120 DEG C of vacuum drying remove solvent and moisture, and pole piece is cut into circular electrode as working electrode.In the hand full of argon gas
In casing, using metal lithium sheet as to electrode, Celgard 2400 is barrier film, 1mol/L LiPF6/EC-EMC-DMC (volumes
Than for 1:1:1) it is electrolyte, is assembled into button cell, stands 8h.In 2.5~4.5V voltage ranges, constant current is carried out with 0.1C
Charge-discharge performance is tested, and discharge capacity is 156.3mAh/g, and voltage is 3.97V, first charge-discharge efficiency 99.5%.
Embodiment 2：
MnPO4·H2Prepared by O nano powders, FePO4·2H2Prepared by O nano powders, the preparation of 5mol/L lithium metal solution is same
Embodiment 1.
The graphene oxide for taking 3.4956g Brodie methods to prepare is added in 200mL methyl ethers, in 40KHz supersonic frequency
Under ultrasonically treated 2h, be made graphene oxide dispersion.By n (Fe)：N (Mn)=5:5 molar ratios weigh 18.6847g respectively
FePO4·2H2O、16.7925g MnPO4·H2Two kinds of nano powders of O are placed in ball grinder, and planet is used in ethanol decentralized medium
Formula ball mill ball milling 4h is mixed evenly, 120 DEG C of dry 6h, and being added to above-mentioned scattered graphene oxide after grinding is uniform disperses
In liquid, continue ultrasonically treated 3h under 40KHz supersonic frequency to being uniformly dispersed.50mL 5mol/L lithium metal solution is taken,
Gradually it is added drop-wise under conditions of magnetic agitation in above-mentioned finely dispersed mixed system.After fully reacting, then it is gradually added into
11.62g expoxy propane, stirring 1h makes complexing completely, and suction filtration, absolute ethyl alcohol wash to obtain presoma.By presoma in 80 DEG C of vacuum
Under the conditions of dry 10h.Grind uniform after drying, then load powder in corundum boat, it is high at a temperature of 760 DEG C in nitrogen
Temperature sintering 8h.Furnace cooling produces the LiFe of graphene coated to room temperature0.5Mn0.5PO4, the covering amount of graphene is 10wt%.
Electrochemical property test method and condition be the same as Example 1, test result is：Discharge capacity is 158.2mAh/g, in
Threshold voltage is 3.94V, first charge-discharge efficiency 99.7%.
Embodiment 3：
MnPO4·H2Prepared by O nano powders, FePO4·2H2Prepared by O nano powders, the preparation of 5mol/L lithium metal solution is same
Embodiment 1.
The graphene oxide for taking 3.4977g Staudenmaier methods to prepare is added in 200mL ether, in the super of 40KHz
Ultrasonically treated 2h under acoustic frequency, is made graphene oxide dispersion.By n (Fe)：N (Mn)=6:4 molar ratios are weighed respectively
22.4216g FePO4·2H2O、13.4340g MnPO4·H2Two kinds of nano powders of O are placed in ball grinder, in ethanol decentralized medium
Middle use planetary ball mill ball milling 4h is mixed evenly, 120 DEG C of dry 6h, and above-mentioned scattered oxidation is added to after grinding is uniform
In graphene dispersing solution, continue ultrasonically treated 3h under 40KHz supersonic frequency to being uniformly dispersed.Take 50mL 5mol/L gold
Belong to lithium solution, be gradually added drop-wise under conditions of magnetic agitation in above-mentioned finely dispersed mixed system.After fully reacting, then
11.62g expoxy propane is gradually added into, stirring 1h makes complexing completely, and suction filtration, absolute ethyl alcohol wash to obtain presoma.Presoma is existed
10h is dried under 80 DEG C of vacuum conditions.Grind uniform after drying, then load powder in corundum boat, in nitrogen, 760 DEG C
At a temperature of, high temperature sintering 8h.Furnace cooling produces the LiFe of graphene coated to room temperature0.6Mn0.4PO4, the covering amount of graphene
For 10wt%.
Electrochemical property test method and condition be the same as Example 1, test result is：Discharge capacity is 158.9mAh/g, electricity
Press as 3.92V, first charge-discharge efficiency 99.7%.
Embodiment 4：
MnPO4·H2Prepared by O nano powders, FePO4·2H2Prepared by O nano powders, the preparation of 5mol/L lithium metal solution is same
Embodiment 1.
Weigh 84.5g MnSO4·H2O is dissolved in 200ml deionized waters, weighs 190.07g Na3PO4·12H2O is dissolved in
In 100ml deionized waters, two kinds of solution are mixed in 1000ml beaker, 300ml acetone are then added, in 60 DEG C of water-baths
1h is stirred vigorously, has precipitation to generate.Gained is precipitated into suction filtration, then washed with deionized water, ethanol 3 times, 80 DEG C of drying, both
MnPO4·H2O nano powders.
Weigh 81.1g FeCl3It is dissolved in 300ml deionized waters, weighs 57.5g NH4H2PO4It is dissolved in 100ml deionized waters
In, two kinds of solution are mixed in 1000ml beaker, 400ml ethanol is then added, is stirred vigorously 4h in 30 DEG C of water-baths, has
Precipitation generation.Gained is precipitated into suction filtration, then washed with deionized water, ethanol 3 times, 80 DEG C of drying both obtain FePO4·2H2O receives
Ground rice.
7g metal lithium sheet is added gradually to fill in the Dewar bottle of 1L glycol dimethyl ethers and dissolved, form 1mol/L's
Blue lithium metal solution, is sealed stand-by.
The graphene oxide for taking 3.91g Hummers methods to prepare is added in 200mL acetone, in 40KHz supersonic frequency
Under ultrasonically treated 2h, be made graphene oxide dispersion.By n (Fe)：N (Mn)=0.25 molar ratio weighs 18.68g respectively
FePO4·2H2O、67.17g MnPO4·H2Two kinds of nano powders of O are placed in ball grinder, using planetary in ethanol decentralized medium
Ball mill ball milling 6h is mixed evenly, 120 DEG C of dry 8h, and above-mentioned scattered graphene oxide dispersion is added to after grinding is uniform
In, continue ultrasonically treated 6h under 40KHz supersonic frequency to being uniformly dispersed.500mL 1mol/L lithium metal solution is taken,
Gradually it is added drop-wise under conditions of magnetic agitation in above-mentioned finely dispersed mixed system.After fully reacting, then it is gradually added into
26.68g acetonitriles, stirring 0.5h makes complexing completely, and suction filtration, absolute ethyl alcohol wash to obtain presoma.By presoma in 60 DEG C of vacuum bars
24h is dried under part.Grind uniform after drying, then load powder in corundum boat, in helium, at a temperature of 600 DEG C, high temperature
Sinter 10h.Furnace cooling produces the LiFe of graphene coated to room temperature0.2Mn0.8PO4, the covering amount of graphene is 5wt%.
Electrochemical property test method and condition be the same as Example 1, test result is：Discharge capacity is 155mAh/g, intermediate value
Voltage is 4.03V.First charge-discharge efficiency 99.3%.
Embodiment 5：
Weigh 125.5045g Mn (NO3)2·4H2O is dissolved in 200ml deionized waters, pipettes 29.10ml H3PO4(density
For 1.685g/ml) it is added in manganese nitrate solution, 200ml ethanol is then added, 3h is stirred vigorously in 45 DEG C of water-baths, there is heavy
Form sediment and generate.Gained is precipitated into suction filtration, then washed with deionized water, ethanol 3 times, 80 DEG C of drying both obtain MnPO4·H2O nanometers
Powder.
Weigh 139.01g FeSO47H2O is dissolved in 300ml deionized waters, weighs 66.03g (NH4)2HPO4It is dissolved in
In 100ml deionized waters, two kinds of solution are mixed in 1000ml beaker, 400ml ethylene glycol, 50 DEG C of water-baths is then added
In be stirred vigorously 2h, have precipitation generate.Gained is precipitated into suction filtration, then washed with deionized water, ethanol 3 times, 80 DEG C of drying, both
Obtain FePO4·2H2O nano powders.
Being added gradually to fill 1L ether and methyl ether mixed liquor by 105g metal lithium sheet, (volume ratio of ether and methyl ether is
1:1) dissolved in Dewar bottle, form 15mol/L blue lithium metal solution, sealed stand-by.
MnPO4·H2Prepared by O nano powders, FePO4·2H2Prepared by O nano powders, the preparation of 5mol/L lithium metal solution is same
Embodiment 1.
The graphene oxide for taking 11.82g Hummers methods to prepare is added in 200mL methyl ethers, in 40KHz supersonic frequency
Under ultrasonically treated 2h, be made graphene oxide dispersion.By n (Fe)：N (Mn)=4:1 molar ratio weighs 74.74g respectively
FePO4·2H2O、16.8g MnPO4·H2Two kinds of nano powders of O are placed in ball grinder, using planetary in ethanol decentralized medium
Ball mill ball milling 2h is mixed evenly, 130 DEG C of dry 4h, and above-mentioned scattered graphene oxide dispersion is added to after grinding is uniform
In, continue ultrasonically treated 3h under 40KHz supersonic frequency to being uniformly dispersed.50mL 15mol/L lithium metal solution is taken,
Gradually it is added drop-wise under conditions of magnetic agitation in above-mentioned finely dispersed mixed system.After fully reacting, then it is gradually added into
43.5g expoxy propane, stirring 2h makes complexing completely, and suction filtration, absolute ethyl alcohol wash to obtain presoma.By presoma in 90 DEG C of vacuum bars
10h is dried under part.Grind uniform after drying, then load powder in corundum boat, in argon gas, at a temperature of 800 DEG C, high temperature
Sinter 4h.Furnace cooling produces the LiFe of graphene coated to room temperature0.8Mn0.2PO4, the covering amount of graphene is 15wt%.
Electrochemical property test method and condition be the same as Example 1, test result is：Discharge capacity is 149mAh/g, intermediate value
Voltage is 3.95V, first charge-discharge efficiency 98.3%.
Comparative example 1
Using the lithium ferric manganese phosphate positive electrode of prior art as positive electrode, electrochemical property test method and condition are same
Embodiment 1.Test result is：Discharge capacity is 148mAh/g, and voltage is 3.94V, first charge-discharge efficiency 97.8%.
From the electrochemical property test data in above-described embodiment 1~5 and comparative example 1, graphene bag of the invention
Cover lithium ferric manganese phosphate positive electrode in terms of existing technologies, discharge capacity and first charge-discharge efficiency are improved.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (9)
1. a kind of graphene coated lithium ferric manganese phosphate positive electrode, it is characterised in that：The graphene coated lithium ferric manganese phosphate is just
The formula of pole material is：LiFexMn1-xPO4/ graphene, it is prepared by following steps：
Step 1：First manganese source and phosphorus source are dissolved in deionized water respectively, and oxidant is added in manganese source solution；Next, according to
Element ratio n（Mn）：n（P）=1:1 measures manganese source solution and phosphorus source solution, is mixed evenly and obtains manganese source and phosphorus source mixing
Solution, adds dispersion liquid, and the volume of the dispersion liquid is identical with the volume of manganese source and phosphorus source mixed solution；Then in water-bath
Stirring generation sediment；MnPO will be obtained after sediment suction filtration, washing and drying4·H2O nano powders；Wherein bath temperature is 30
~60 DEG C, 1~4h of mixing time；
Step 2：Source of iron and phosphorus source are dissolved in deionized water respectively, when source of iron is ferrous iron, oxidation is added in source of iron solution
Agent；According to element ratio n（Fe）：n（P）=1:1 measures under source of iron solution and phosphorus source solution, stirring condition, by phosphorus source solution gradually
Instill in source of iron solution and obtain source of iron and phosphorus source mixed solution, add dispersion liquid, volume and source of iron and the phosphorus of the dispersion liquid
The volume of source mixed solution is identical；Then sediment is generated in stirred in water bath；It will be obtained after sediment suction filtration, washing and drying
FePO4·2H2O nano powders；Wherein bath temperature is 30~60 DEG C, 1~4h of mixing time；
Step 3：Lithium metal is added in nonaqueous solvents and dissolved, 1~15mol/L lithium solution is formed, sealed stand-by；
Step 4：Add graphene oxide into dispersion solvent, 0.01~0.05g/mL of formation suspension, ultrasonically treated 2~
4h, obtains graphene oxide dispersion, wherein supersonic frequency is 30 ~ 60KHz；
Step 5：By MnPO described in step 14·H2FePO described in O and step 24·2H2Two kinds of nano powders of O press n（Fe）：n（Mn）=
0.25~4.0 mol ratio is placed in ball grinder, is added decentralized medium, preferably just submerging powder, is used ball mill ball milling
It is mixed evenly, is dried to obtain mixed powder, wherein 2~6h of Ball-milling Time, 110 ~ 130 DEG C of drying temperature, 4~8h of drying time；
Step 6：Step 5 mixed powder is added in the graphene oxide dispersion in step 4 carry out it is ultrasonically treated to scattered
Uniformly, mixed system is obtained, the numerical value of the quality of graphene oxide in grams is mixed wherein in graphene oxide dispersion
Close powder integral molar quantity numerical value 7.82 ~ 23.64 times, 3~6h of sonication treatment time, supersonic frequency is 30 ~ 60KHz；
Step 7：Lithium solution described in step 3 is gradually dropped in the finely dispersed mixed system of step 6 under stirring condition, stirring is extremely
Reaction is complete, and the mole that wherein lithium GOLD FROM PLATING SOLUTION belongs to lithium is 1~1.5 times of the integral molar quantity of mixed powder described in step 5；
Step 8：Under stirring condition, addition lithium complexing agent in complete mixed system is reacted to step 7,0.5~2h of stirring makes network
Close complete, filtering, washing obtain presoma, the wherein amount of lithium complexing agent belongs to lithium for the lithium GOLD FROM PLATING SOLUTION added in the step 7
1~1.3 times of mole；
Step 9：Presoma described in step 8 is dried in vacuo, then ground uniformly into powder, then loads powder in corundum boat,
Room temperature is cooled to the furnace after sintering in an inert atmosphere, graphene coated lithium ferric manganese phosphate positive electrode is obtained, and wherein vacuum is done
Dry temperature is 60~90 DEG C, 10~24h of drying time, 600~800 DEG C of sintering temperature, 4~10h of sintering time；
Wherein, the manganese source is that manganese acetate, manganese oxalate, formic acid manganese, manganese sulfate, manganese nitrate and manganese chloride solubility contain manganese compound
At least one of；
Phosphorus source is phosphoric acid, ammonium phosphate, Diammonium phosphate (DAP), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, phosphorus
At least one of soluble phosphorus-containing compound of sour hydrogen dipotassium, sodium phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate；
The source of iron is iron chloride, ferric sulfate, ferric nitrate, frerrous chloride, ferrous sulfate, ferrous nitrate, ferrous oxalate, acetic acid Asia
At least one of soluble iron containing compoundses of iron, ferrous bromide；
The oxidant is H2O2、Na2O2, nitric acid, the concentrated sulfuric acid, at least one of HClO and NaClO；
The dispersion liquid be absolute ethyl alcohol, acetone, ethylene glycol, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol,
At least one of cellulose derivative, polyacrylamide, guar gum and fatty acid polyethylene glycol ester；
The lithium metal is at least one of metallic lithium powder, metal lithium sheet, block lithium and lithium silk；
The nonaqueous solvents be liquefied ammonia, glycol dimethyl ether, tetrahydrofuran, ether, methyl ether or dimethyl acetamide at least
It is a kind of；
The dispersion solvent is at least one of methyl ether, ether or acetone；
The decentralized medium is at least one of ethanol, ethylene glycol and acetone；
The complexing agent is at least one of expoxy propane, acetonitrile, 12-crown-4 and dimethyl sulfoxide (DMSO)；
The inert atmosphere is at least one of helium, argon gas or nitrogen；
The scope of the x is 0.2≤x≤0.8.
2. graphene coated lithium ferric manganese phosphate positive electrode according to claim 1, it is characterised in that：Described in step 5
MnPO4·H2FePO described in O and step 24·2H2The mol ratio of two kinds of nano powders of O is n（Fe）：n（Mn）=0.5~3.0.
3. graphene coated lithium ferric manganese phosphate positive electrode according to claim 2, it is characterised in that：Described in step 5
MnPO4·H2FePO described in O and step 24·2H2The mol ratio of two kinds of nano powders of O is n（Fe）：n（Mn）=4:6 or 5:5 or 6:4.
4. the graphene coated lithium ferric manganese phosphate positive electrode according to claim 1 ~ 3 any one, it is characterised in that：Step
The mole that lithium GOLD FROM PLATING SOLUTION described in rapid 7 belongs to lithium is 1.1~1.3 times of the integral molar quantity of mixed powder described in step 5.
5. the graphene coated lithium ferric manganese phosphate positive electrode according to claim 1 ~ 3 any one, it is characterised in that：Step
The amount of lithium complexing agent described in rapid 8 is the lithium GOLD FROM PLATING SOLUTION that adds belongs to lithium mole in the step 7 1~1.2 times.
6. the graphene coated lithium ferric manganese phosphate positive electrode according to claim 1 ~ 3 any one, it is characterised in that：Step
The mole specific concentration of lithium solution described in rapid 3 is 1~10mol/L.
7. graphene coated lithium ferric manganese phosphate positive electrode according to claim 6, it is characterised in that：Lithium described in step 3
The mole specific concentration of solution is 1~5mol/L.
8. the graphene coated lithium ferric manganese phosphate positive electrode according to claim 1 ~ 3 any one, it is characterised in that：Step
Rapid 1 and step 2 described in bath temperature be 40~50 DEG C, 2~3h of mixing time；2 ~ 3h of sonication treatment time described in step 4, step
2~4h of sonication treatment time described in 6, supersonic frequency described in step 4 and step 6 is 40 ~ 50KHz；Ball-milling Time 3 described in step 5
~5h, the ball mill is planetary ball mill, 110 ~ 120 DEG C of the drying temperature, the 3~6h of drying time；Step 7 and
The mode of stirring condition described in step 8 is magnetic agitation, and speed of agitator is 100~400r/min；Temperature is dried in vacuo described in step 9
Spend for 70~80 DEG C, 12~20h of drying time, 600~800 DEG C of sintering temperature, 3~8h of sintering time.
9. a kind of preparation method of graphene coated lithium ferric manganese phosphate positive electrode as claimed in claim 1, it is characterised in that
Comprise the steps of：
Step 1：First manganese source and phosphorus source are dissolved in deionized water respectively, and oxidant is added in manganese source solution；Next, according to
Element ratio n（Mn）：n（P）=1:1 measures manganese source solution and phosphorus source solution, is mixed evenly and obtains manganese source and phosphorus source mixing
Solution, adds dispersion liquid, and the volume of the dispersion liquid is identical with the volume of manganese source and phosphorus source mixed solution；Then in water-bath
Stirring generation sediment；MnPO will be obtained after sediment suction filtration, washing and drying4·H2O nano powders；Wherein bath temperature is 30
~60 DEG C, 1~4h of mixing time；
Step 2：Source of iron and phosphorus source are dissolved in deionized water respectively, when source of iron is ferrous iron, oxidation is added in source of iron solution
Agent；According to element ratio n（Fe）：n（P）=1:1 measures under source of iron solution and phosphorus source solution, stirring condition, by phosphorus source solution gradually
Instill in source of iron solution and obtain source of iron and phosphorus source mixed solution, add dispersion liquid, volume and source of iron and the phosphorus of the dispersion liquid
The volume of source mixed solution is identical；Then sediment is generated in stirred in water bath；It will be obtained after sediment suction filtration, washing and drying
FePO4·2H2O nano powders；Wherein bath temperature is 30~60 DEG C, 1~4h of mixing time；
Step 3：Lithium metal is added in nonaqueous solvents and dissolved, 1~15mol/L lithium solution is formed, sealed stand-by；
Step 4：Add graphene oxide into dispersion solvent, 0.01~0.05g/mL of formation suspension, ultrasonically treated 2~
4h, obtains graphene oxide dispersion, wherein supersonic frequency is 30 ~ 60KHz；
Step 5：By MnPO described in step 14·H2FePO described in O and step 24·2H2Two kinds of nano powders of O press n（Fe）：n（Mn）=
0.25~4.0 mol ratio is placed in ball grinder, is added decentralized medium, preferably just submerging powder, is used ball mill ball milling
It is mixed evenly, is dried to obtain mixed powder, wherein 2~6h of Ball-milling Time, 110 ~ 130 DEG C of drying temperature, 4~8h of drying time；
Step 6：Step 5 mixed powder is added in the graphene oxide dispersion in step 4 carry out it is ultrasonically treated to scattered
Uniformly, mixed system is obtained, the numerical value of the quality of graphene oxide in grams is mixed wherein in graphene oxide dispersion
Close powder integral molar quantity numerical value 7.82 ~ 23.64 times, 3~6h of sonication treatment time, supersonic frequency is 30 ~ 60KHz；
Step 7：Lithium solution described in step 3 is gradually dropped in the finely dispersed mixed system of step 6 under stirring condition, stirring is extremely
Reaction is complete, and the mole that wherein lithium GOLD FROM PLATING SOLUTION belongs to lithium is 1~1.5 times of the integral molar quantity of mixed powder described in step 5；
Step 8：Under stirring condition, addition lithium complexing agent in complete mixed system is reacted to step 7,0.5~2h of stirring makes network
Close complete, filtering, washing obtain presoma, the wherein amount of lithium complexing agent belongs to lithium for the lithium GOLD FROM PLATING SOLUTION added in the step 7
1~1.3 times of mole；
Step 9：Presoma described in step 8 is dried in vacuo, then ground uniformly into powder, then loads powder in corundum boat,
Room temperature is cooled to the furnace after sintering in an inert atmosphere, graphene coated lithium ferric manganese phosphate positive electrode is obtained, and wherein vacuum is done
Dry temperature is 60~90 DEG C, 12~24h of drying time, 600~800 DEG C of sintering temperature, 4~10h of sintering time；
Wherein, the manganese source is that manganese acetate, manganese oxalate, formic acid manganese, manganese sulfate, manganese nitrate and manganese chloride solubility contain manganese compound
At least one of；
Phosphorus source is phosphoric acid, ammonium phosphate, Diammonium phosphate (DAP), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, phosphorus
At least one of soluble phosphorus-containing compound of sour hydrogen dipotassium, sodium phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate；
The source of iron is iron chloride, ferric sulfate, ferric nitrate, frerrous chloride, ferrous sulfate, ferrous nitrate, ferrous oxalate, acetic acid Asia
At least one of soluble iron containing compoundses of iron, ferrous bromide；
The oxidant is H2O2、Na2O2, nitric acid, the concentrated sulfuric acid, at least one of HClO and NaClO；
The dispersion liquid be absolute ethyl alcohol, acetone, ethylene glycol, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol,
At least one of cellulose derivative, polyacrylamide, guar gum and fatty acid polyethylene glycol ester；
The lithium metal is at least one of metallic lithium powder, metal lithium sheet, block lithium and lithium silk；
The nonaqueous solvents be liquefied ammonia, glycol dimethyl ether, tetrahydrofuran, ether, methyl ether or dimethyl acetamide at least
It is a kind of；
The dispersion solvent is at least one of methyl ether, ether or acetone；
The decentralized medium is at least one of ethanol, ethylene glycol and acetone；
The complexing agent is at least one of expoxy propane, acetonitrile, 12-crown-4 and dimethyl sulfoxide (DMSO)；
The inert atmosphere is at least one of helium, argon gas or nitrogen.
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