CN103928680A - Spray drying auxiliary synthesis method for preparing sheet type lithium manganese phosphate/graphene composite material - Google Patents
Spray drying auxiliary synthesis method for preparing sheet type lithium manganese phosphate/graphene composite material Download PDFInfo
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Abstract
The invention relates to a spray drying auxiliary synthesis method for preparing a sheet type lithium manganese phosphate/graphene composite material, belonging to the technical field of lithium ion battery electrode materials. The method disclosed by the invention mainly comprises the following steps of dissolving a lithium source, a manganese source and a phosphorus source into a three-neck circular-bottom flask with a proper amount of an organic solvent according to the mole ratio of (1.0-1.1) to 1 to 1, heating the mixture to 50-150 DEG C, and keeping for 2-6 hours to obtain a sheet type pure phase lithium manganese phosphate material; dispersing the sheet type pure phase lithium manganese phosphate material into an organic carbon source, performing ultrasonic treatment, drying, and pre-sintering at the temperature of 300-600 DEG C to obtain sheet type lithium manganese phosphate covered with the organic carbon source; then mixing with a fixed amount of a graphene oxide aqueous solution, and performing stirring and ultrasonic treatment, performing spray drying at the temperature of 140-250 DEG C, and sintering at high temperature to obtain a product. Due to the lithium manganese phosphate/graphene sheet composite structure, the structural stability and conductivity of the composite material are improved; according to the spray drying method, the tap density and volume ratio energy of the material are greatly improved; furthermore, reaction raw materials of the experiment are readily available, the method is simple, the operation is simple, and the spray drying auxiliary synthesis method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, particularly a kind of method of the dry auxiliary synthesizing flaky lithium manganese phosphate/graphene composite material of spraying.Belong to lithium ion battery electrode material technical field.
Background technology
At present, the fossil energies such as coal, oil, natural gas are day by day exhausted, and the problem of environmental pollution bringing is thus on the rise, and therefore, the preferential technology with giving priority to raising energy utilization rate and the new clean energy resource of exploitation has become the development strategic objective of national governments.New forms of energy mainly comprise the clean energy resourcies such as solar energy, wind energy, biomass energy, nuclear energy and ocean tidal power, and these energy have the features such as discontinuity and unsteadiness, therefore will make full use of conversion and the storage that new forms of energy just relate to energy efficient rate.Chemical power source can be realized conversion, the storage power between chemical energy and electric energy, plays vital effect in people's productive life.
The many merits such as lithium ion battery has that voltage is high, good cycle, energy density are large, memory-less effect, self discharge is little, operating temperature range is wide are green high-capacity batteries of new generation.At present, the application of lithium ion battery constantly expands, and has become the important content to the significant new high-tech product of national economy.
Positive electrode has determined the performance of lithium ion battery to a great extent, thereby is the study hotspot of domestic and international lithium ion battery circle always.Overwhelming majority research work concentrates on the lithium intercalation compound of period 4 Ti, V, Mn, Fe, Co, 6 kinds of variable valency transition metals of Ni.First generation positive electrode is metal sulfide, as TiS
2, MoS
2deng.Second generation positive electrode is lithium-compound transition metal oxide, with LiCoO
2for representative, comprise LiNiO
2, LiMnO
2, LiMn
2o
4, LiV
3o
8, LiNi
xco
1-xo
2, LiNi
1/3co
1/3mn
1/3o
2and various derivatives.Third generation positive electrode is with LiFePO
4polyanion type compound-material for representative.Compare with lithium-compound transition metal oxide material, it is stable that polyanion type compound positive electrode generally has crystal structure, Heat stability is good, and the excellent outstanding advantages that waits of security performance, can be applicable to power type and accumulation energy type lithium ion battery.
We know, by controlling particle size and surperficial coated with conductive carbon-coating, LiFePO
4the high rate performance of positive electrode has reached excellent level, thereby is considered to very practical positive electrode.However, with other positive electrode as LiCoO
2, LiNiCoO
2and Li
2mnO
4deng comparing, LiFePO
4discharge platform very low, only have the relative Li/Li of 3.4 V(
+).And with the LiMnPO of its structural similarity
4discharge platform reach 4.1 V, compare LiFePO
4high 0.65 V, and can in current existing electrolyte solution, stablize use; In addition LiMnPO,
4energy density be 697 Wh/kg, be LiFePO
41.2 times of energy density (586 Wh/kg), so be considered to a kind of positive electrode of having very much potentiality.But LiMnPO
4very low lithium ion diffusion coefficient and compare LiFePO
4lower electronic conductivity (compares LiFePO
4low 5 orders of magnitude), limited its large-scale application.
For above-mentioned shortcoming, researcher takes the whole bag of tricks to LiMnPO
4carry out modification, mainly comprise and reduce particle size, cation doping, the LiMnPO to pure phase
4carry out carbon and be coated, directly synthesize LiMnPO
4/ C compound.In the means of these modifications, reducing particle size and carbon coated is topmost method.However, the LiMnPO of preparation
4material does not also reach the instructions for use of commercial battery far away.
The synthetic method of lithium manganese phosphate mainly contains high temperature solid-state method, carbothermic method, sol-gal process and microwave method at present.The advantage of high temperature solid-state method is that technique is simple, easily realizes industrialization, but the purity of synthetic sample is not high, particle diameter is large, chemical property is poor, and traditional high temperature solid-state method is with H
2or with other inert gas (N
2, mixture Ar), as reducing agent, exists high, the unsafe shortcoming of cost.Though carbothermic method can reduce costs and improve material property, adopt the still mixing inequality of inevitable raw material of the hot solid phase reduction of carbon, affect the tap density of positive electrode.Although sol-gel process synthesis temperature is low, product cut size is little, chemical property and good cycling stability, operate more complicated, severe reaction conditions.Microwave method has short, low power consumption and other advantages of reaction time, but heating time is wayward.Research in recent years shows, grapheme material modification lithium-ion battery material demonstrates splendid effect, with the LiFePO of Graphene modification
4there is great raising with metal oxide materials specific discharge capacity and cycle life.In research before us, the Li of Graphene modification
3v
2(PO
4)
3material electrochemical performance has also obtained improving largely, is mainly because Graphene has higher electronic conductivity and structural stability compared with RESEARCH OF PYROCARBON, therefore can be used for LiMnPO
4the modification of based composites.
Summary of the invention
The object of the invention is to, for the shortcoming of prior art, provide a kind of method of the synthetic manganese-lithium phosphate anode material of the dry assisted Solid-state method of spraying of applicable suitability for industrialized production.Effectively control the chemical composition of lithium manganese phosphate, the pattern of material and particle diameter and carbon content, improve its stability and electric conductivity, the multiplying power of improving material charges and discharge and cycle performance.
For achieving the above object, the present invention adopts following technical scheme:
The dry assisted synthesizing method of spraying of preparing sheet lithium manganese phosphate/graphene composite material, is characterized in that comprising the steps:
(a) synthesizing flaky pure phase lithium manganese phosphate: be that 1.0 ~ 1.1:1:1 is dissolved into manganese source in certain deionized water according to the mol ratio of stoichiometric proportion lithium, manganese, phosphorus, then join in the three neck round-bottomed flasks that fill appropriate organic solvent, the mixed solution obtaining is fully being heated to 90 ~ 150 ℃ of maintenance 1 ~ 5 h under stirring state.Rate of addition with 1 ~ 5 mL/min dropwise adds quantitative He Lin source, lithium source mixed aqueous solution in above-mentioned solution again, after dripping, it is kept at this temperature to naturally cooling after 2 ~ 6 h.By the solution centrifugal obtaining, with deionized water and ethanol alternately washing each three times to remove remaining organic solvent, 60 ~ 100 ℃ of oven dry of spending the night; Li source compound described in step is lithium sulfate; Manganese source compound is manganese sulfate; P source compound is triammonium phosphate; Described organic solvent is diethylene glycol;
(b) carbon is coated: get quantitative organic carbon source in appropriate organic solvent, dissolve the backward sheet pure phase lithium manganese phosphate that it adds quantitative step (1) to obtain, the mass ratio of the quality of described carbon source and sheet lithium manganese phosphate is 1:20 ~ 1:10; Ultrasonic 10 ~ 60 min, obtain the coated sheet lithium manganese phosphate of organic carbon source after oven dry.Again by the solid abrasive obtaining to powder, proceed in tube furnace, under inert atmosphere, with the programming rate of 1 ~ 30 ℃/min, gas flow rate is 10 ~ 50 mL/min, is heated to 300 ~ 600 ℃ and keeps 2 ~ 8 h, obtains the coated sheet lithium manganese phosphate of carbon; Organic carbon source described in step is glucose; Organic solvent is methyl alcohol; The source of the gas of inert atmosphere is selected from nitrogen;
(c) compound with Graphene: the sheet lithium manganese phosphate that above-mentioned steps (b) is obtained joins the quantitative graphene oxide aqueous solution and stirs 1 ~ 4 h, then it is dry after ultrasonic 10 ~ 60 min, at 140 ~ 250 ℃, to spray; Graphene oxide described in step is the synthetic graphene oxide aqueous solution of chemical oxidization method; The addition of graphene oxide is 1% ~ 5% of above-mentioned steps (b) lithium manganese phosphate weight;
(d) calcination reaction: above-mentioned steps (c) resulting materials is proceeded in tube furnace, under nitrogen inert atmosphere with the programming rate of 1 ~ 30 ℃/min, gas flow rate is 10 ~ 50 mL/min, is warmed up to 400 ~ 800 ℃ and keeps 2 ~ 8 h to obtain product sheet lithium manganese phosphate/Graphene.
Li source compound described in the inventive method is except lithium sulfate, and also available lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium hydroxide substitute; Described manganese source compound is except manganese sulfate, and also available manganese nitrate, manganese acetate, manganese chloride, manganese carbonate substitute; Described P source compound is except triammonium phosphate, and also phosphoric acid ammonium dihydrogen, diammonium hydrogen phosphate substitute; Described organic solvent, also can spent glycol, butanols substitutes except diethylene glycol.Described organic carbon source is except glucose, and also available polypropylene, sucrose, polystyrene substitute.
advantage and disadvantage of the present invention
With other lithium manganese phosphate, lithium manganese phosphate/graphene composite material is compared, and this nano composite material that we prepare has following outstanding feature:
(1) with an organic solvent by circumfluence method, synthesize lithium manganese phosphate, material thing phase purity is high, XRD diffraction phase free from foreign meter.
(2), by be coated to keep the laminated structure of pure phase lithium manganese phosphate with organic carbon source, avoid stirring with the graphene oxide aqueous solution, laminated structure goes to pot in ultrasonic procedure.
(3) in follow-up spray-drying process, the fold Graphene that lithium manganese phosphate and graphene oxide pyrolysis obtain is interweaved and is intertwined, and forms the compound structure of sheet-sheet.On the one hand, the amorphous carbon that organic carbon source carbonization generates is conducive to improve the conductivity of lithium manganese phosphate, and can limit the growth of lithium manganese phosphate.On the other hand, sheet-sheet composite construction is more conducive to keep the structural stability of material, serves as the conducting matrix grain of lithium manganese phosphate material through the Graphene of the dry fold obtaining of spraying.These have all improved conductivity and the lithium ion diffusion rate of composite material electronics greatly.
(4) adopt the dry auxiliary synthesizing graphite alkene of spraying and the coated lithium manganese phosphate of organic carbon, the content of carbon is easy to control, the winding that is interweaved of the Graphene forming after calcining and lithium manganese phosphate, this structure is highly stable, and preparation technology is simple, operation is controlled easily, easily realizes suitability for industrialized production.
(5) the coated lithium manganese phosphate composite material charge/discharge capacity of Graphene and organic carbon is high, good rate capability, and cycle performance is excellent.The synthetic lithium manganese phosphate obtaining is assembled into half-cell and tests together with lithium sheet, and voltage range is at 2.5~4.4 V, and with 0.05 C rate charge-discharge, discharge capacity reaches 105.1 mAh/g; With 0.1C multiplying power discharging, discharge capacity approaches 95.3 mAh/g.0.05 C discharges and recharges after 50 circulations, and capability retention reaches 91.4%, only has a small amount of decay.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of embodiment 1 and embodiment 2 preparation sheet lithium manganese phosphate/graphene composite materials, wherein: a is the X ray diffracting spectrum of embodiment 1; B is the X ray diffracting spectrum of embodiment 2.
Fig. 2 is the SEM figure that embodiment 2 prepares lithium manganese phosphate/graphene composite material.
Fig. 3 is the TEM figure that embodiment 3 prepares lithium manganese phosphate/graphene composite material.
Fig. 4 is that embodiment 1 prepares the first charge-discharge curve of lithium manganese phosphate/graphene composite material under 2.5~4.4 V voltage range different multiplying, wherein: discharge-rate is respectively 0.05C, 0.1C, 0.2C, 0.5C and 1C.
Fig. 5 is that embodiment 4 prepares the cycle performance figure of lithium manganese phosphate/graphene composite material under 2.5~4.4 V voltage range 0.05C multiplying powers.
Embodiment
Below by embodiment, further illustrate the inventive method.
embodiment 1
According to stoichiometric proportion (mol ratio of lithium, manganese, phosphorus is 1:1:1), manganese nitrate is dissolved in certain deionized water, then join in the three neck round-bottomed flasks that include appropriate diethylene glycol, the mixed solution obtaining is fully being heated to 100 ℃ of maintenance 2 h under stirring state.Rate of addition with 1 mL/min dropwise adds quantitative lithium hydroxide and ammonium dihydrogen phosphate aqueous solution in above-mentioned solution again, after dripping, it is kept at 100 ℃ to naturally cooling after 2 h.By the solution centrifugal obtaining, with deionized water and ethanol, alternately washing each three times is to remove remaining organic solvent, 60 ℃ are spent the night to dry and obtain sheet pure phase lithium manganese phosphate; Get quantitative glucose in appropriate organic solvent, dissolve backward its and add quantitative pure phase lithium manganese phosphate, ultrasonic 30 min, obtain the coated sheet lithium manganese phosphate of organic carbon source after oven dry.Again by the solid abrasive obtaining to powder, proceed in tube furnace, under nitrogen atmosphere, with the programming rate of 1 ℃/min, gas flow rate is 10 mL/min, is heated to 400 ℃ and keeps 2 h, obtains the coated lithium manganese phosphate of carbon; The coated lithium manganese phosphate of carbon is joined to the synthetic graphene oxide aqueous solution of quantitative chemical oxidizing process and stir 1 h, then it is dry after ultrasonic 10 min, at 200 ℃, to spray; Above-mentioned resulting materials is proceeded in tube furnace, and under nitrogen atmosphere, with the programming rate of 5 ℃/min, gas flow rate is 10 mL/min, is warmed up to 400 ℃ and keeps 8 h to obtain product lithium manganese phosphate/Graphene.Recording the material that this spray-on process obtains is lithium manganese phosphate and graphene film sheet composite construction, and tap density is 1.40 g/cm
3.
The XRD of product is shown in Fig. 1 shown in a curve, as seen from the figure, adopts the dry auxiliary solid phase synthesis process of spraying, has prepared the manganese-lithium phosphate anode material of pure phase, does not have impurity peaks to appear in the diffraction maximum of XRD.Take lithium sheet as negative pole, the product of gained is assembled into half-cell and carries out experiment test, by rate charge-discharge, test its specific discharge capacity (see figure 4).As shown in Figure 4, discharge-rate is 0.05C, and when charging/discharging voltage is 2.5~4.4 V, half-cell specific discharge capacity reaches 105.1 mAh/g, and when discharge-rate increases to 1C, specific discharge capacity is reduced to 60.2 mAh/g.
embodiment 2
According to stoichiometric proportion (mol ratio of lithium, manganese, phosphorus is 1.02:1:1), manganese acetate is dissolved in certain deionized water, then join in the three neck round-bottomed flasks that include appropriate diethylene glycol, the mixed solution obtaining is fully being heated to 125 ℃ of maintenance 5 h under stirring state.Rate of addition with 2 mL/min dropwise adds quantitative lithium chloride and ammonium dihydrogen phosphate aqueous solution in above-mentioned solution again, after dripping, it is kept at this temperature to naturally cooling after 5 h.By the solution centrifugal obtaining, with deionized water and ethanol, alternately washing each three times is to remove remaining organic solvent, 80 ℃ are spent the night to dry and obtain pure phase lithium manganese phosphate; Get quantitative polystyrene in appropriate organic solvent, dissolve backward its and add quantitative pure phase lithium manganese phosphate, ultrasonic 20 min, obtain the coated sheet lithium manganese phosphate of organic carbon source after oven dry.Again by the solid abrasive obtaining to powder, proceed in tube furnace, under nitrogen atmosphere, with the programming rate of 30 ℃/min, gas flow rate is 50 mL/min, is heated to 600 ℃ and keeps 2 h, obtains the coated lithium manganese phosphate of carbon; The coated lithium manganese phosphate of carbon is joined to the synthetic graphene oxide aqueous solution of quantitative chemical oxidizing process and stir 2 h, then it is dry after ultrasonic 15 min, at 140 ℃, to spray; Above-mentioned resulting materials is proceeded in tube furnace, and under nitrogen atmosphere, with the programming rate of 10 ℃/min, gas flow rate is 50 mL/min, is warmed up to 550 ℃ and keeps 4 h to obtain product lithium manganese phosphate/Graphene.
The XRD of product is shown in Fig. 1 shown in b curve equally also do not have impurity phase to occur.Stereoscan photograph is shown in Fig. 2, lithium manganese phosphate is through spraying after dry and high-temperature calcination, fold, curling graphene nanometer sheet generate, lateral dimension is about 1 μ m, the graphene nanometer sheet of fold and lithium manganese phosphate nanometer sheet are interweaved and are intertwined, and in compound, do not have the independent lithium manganese phosphate nanometer sheet together with reuniting.
embodiment 3
According to stoichiometric proportion (mol ratio of lithium, manganese, phosphorus is 1.05:1:1), manganese sulfate is dissolved in certain deionized water, then join in the three neck round-bottomed flasks that include appropriate diethylene glycol, the mixed solution obtaining is fully being heated to 130 ℃ of maintenance 1.5 h under stirring state.Rate of addition with 5 mL/min dropwise adds quantitative lithium hydroxide and ammonium dibasic phosphate aqueous solution in above-mentioned solution again, after dripping, it is kept at 130 ℃ to naturally cooling after 4 h.By the solution centrifugal obtaining, with deionized water and propyl alcohol, alternately washing each three times is to remove remaining organic solvent, 100 ℃ are spent the night to dry and obtain pure phase lithium manganese phosphate; Get quantitative polypropylene in appropriate organic solvent, dissolve backward its and add quantitative pure phase lithium manganese phosphate, ultrasonic 10 min, obtain the coated sheet lithium manganese phosphate of organic carbon source after oven dry.Again by the solid abrasive obtaining to powder, proceed in tube furnace, under nitrogen atmosphere, with the programming rate of 15 ℃/min, gas flow rate is 40 mL/min, is heated to 300 ℃ and keeps 8 h, obtains the coated lithium manganese phosphate of carbon; The coated lithium manganese phosphate of carbon is joined to the synthetic graphene oxide aqueous solution of quantitative chemical oxidizing process and stir 2 h, then it is dry after ultrasonic 10 min, at 250 ℃, to spray; Above-mentioned resulting materials is proceeded in tube furnace, and under nitrogen atmosphere, with the programming rate of 15 ℃/min, gas flow rate is 50 mL/min, is warmed up to 800 ℃ and keeps 2 h to obtain product lithium manganese phosphate/Graphene.Record this material lateral dimension and be about 300 nm, tap density is 1.50 g/cm
3.
Fig. 3 is shown in by the TEM photo of product, can clearly see that graphene film forms the structure of fold, lithium manganese phosphate weave in sheet, the size of sheet lithium manganese phosphate is at 100 ~ 200 nm, after polystyrene carbonization, form the surface that carbon-coating is coated on lithium manganese phosphate, Graphene has formed the conductive network structure of.
embodiment 4
According to stoichiometric proportion (mol ratio of lithium, manganese, phosphorus is 1.1:1:1), manganese chloride is dissolved in certain deionized water, then join in the three neck round-bottomed flasks that include appropriate diethylene glycol, the mixed solution obtaining is fully being heated to 150 ℃ of maintenance 1 h under stirring state.Rate of addition with 4 mL/min dropwise adds quantitative lithium carbonate and the triammonium phosphate aqueous solution in above-mentioned solution again, after dripping, it is kept at this temperature to naturally cooling after 6 h.By the solution centrifugal obtaining, with deionized water and ethylene glycol, alternately washing each three times is to remove remaining organic solvent, 100 ℃ are spent the night to dry and obtain pure phase lithium manganese phosphate; Get quantitative sucrose in appropriate organic solvent, dissolve backward its and add quantitative pure phase lithium manganese phosphate, ultrasonic 60 min, obtain the coated sheet lithium manganese phosphate of organic carbon source after oven dry.Again by the solid abrasive obtaining to powder, proceed in tube furnace, under nitrogen atmosphere, with the programming rate of 10 ℃/min, gas flow rate is 50 mL/min, is heated to 450 ℃ and keeps 5 h, obtains the coated lithium manganese phosphate of carbon; The coated lithium manganese phosphate of carbon is joined to the synthetic graphene oxide aqueous solution of quantitative chemical oxidizing process and stir 4 h, then it is dry after ultrasonic 60 min, at 160 ℃, to spray; Above-mentioned resulting materials is proceeded in tube furnace, and under nitrogen atmosphere, with the programming rate of 1 ℃/min, gas flow rate is 20 mL/min, is warmed up to 650 ℃ and keeps 6 h to obtain product lithium manganese phosphate/Graphene.The size of sheet lithium manganese phosphate is at 200 ~ 300 nm, and tap density is 1.55 g/cm
3.
Take lithium sheet as negative pole, the product of gained is assembled into half-cell in glove box and carries out experiment test, its cycle performance is shown in Fig. 5.At 2.5~4.4 V voltage ranges, discharge and recharge, this lithium manganese phosphate/graphene composite material under 0.05 C multiplying power after 50 circulations discharge capacity retention rate reach 91.4%.
Claims (2)
1. the dry assisted synthesizing method of spraying of preparing sheet lithium manganese phosphate/graphene composite material, is characterized in that comprising the steps:
(a) synthesizing flaky pure phase lithium manganese phosphate: be that 1.0 ~ 1.1:1:1 is dissolved into manganese source in certain deionized water according to the mol ratio of stoichiometric proportion lithium, manganese, phosphorus, then join in the three neck round-bottomed flasks that fill appropriate organic solvent, the mixed solution obtaining is fully being heated to 90 ~ 150 ℃ of maintenance 1 ~ 5 h under stirring state; Rate of addition with 1 ~ 5 mL/min dropwise adds quantitative He Lin source, lithium source mixed aqueous solution in above-mentioned solution again, after dripping, it is kept at this temperature to naturally cooling after 2 ~ 6 h; By the solution centrifugal obtaining, with deionized water and ethanol alternately washing each three times to remove remaining organic solvent, 60 ~ 100 ℃ of oven dry of spending the night; Li source compound described in step is lithium sulfate; Manganese source compound is manganese sulfate; P source compound is triammonium phosphate; Described organic solvent is diethylene glycol;
(b) carbon is coated: get quantitative organic carbon source in appropriate organic solvent, dissolve the backward sheet pure phase lithium manganese phosphate that it adds quantitative step (1) to obtain, the mass ratio of the quality of described carbon source and sheet lithium manganese phosphate is 1:20 ~ 1:10; Ultrasonic 10 ~ 60 min, obtain the coated sheet lithium manganese phosphate of organic carbon source after oven dry; Again by the solid abrasive obtaining to powder, proceed in tube furnace, under inert atmosphere, with the programming rate of 1 ~ 30 ℃/min, gas flow rate is 10 ~ 50 mL/min, is heated to 300 ~ 600 ℃ and keeps 2 ~ 8 h, obtains the coated sheet lithium manganese phosphate of carbon; Organic carbon source described in step is glucose; Organic solvent is methyl alcohol; The source of the gas of inert atmosphere is selected from nitrogen;
(c) compound with Graphene: the sheet lithium manganese phosphate that above-mentioned steps (b) is obtained joins the quantitative graphene oxide aqueous solution and stirs 1 ~ 4 h, then it is dry after ultrasonic 10 ~ 60 min, at 140 ~ 250 ℃, to spray; Graphene oxide described in step is the synthetic graphene oxide aqueous solution of chemical oxidization method; The addition of graphene oxide is 1% ~ 5% of above-mentioned steps (b) lithium manganese phosphate weight;
(d) calcination reaction: above-mentioned steps (c) resulting materials is proceeded in tube furnace, under nitrogen inert atmosphere with the programming rate of 1 ~ 30 ℃/min, gas flow rate is 10 ~ 50 mL/min, is warmed up to 400 ~ 800 ℃ and keeps 2 ~ 8 h to obtain product sheet lithium manganese phosphate/Graphene.
2. a kind of dry assisted synthesizing method of spraying of preparing sheet lithium manganese phosphate/graphene composite material as claimed in claim 1, is characterized in that described Li source compound is except lithium sulfate, and also available lithium nitrate, lithium carbonate, lithium chloride, lithium hydroxide substitute; Described manganese source compound is except manganese sulfate, and also available manganese nitrate, manganese acetate, manganese chloride, manganese carbonate substitute; Described P source compound is except triammonium phosphate, and also phosphoric acid ammonium dihydrogen, diammonium hydrogen phosphate substitute; Described organic solvent, also can spent glycol, butanols substitutes except diethylene glycol; Described organic carbon source is except glucose, and also available polypropylene, sucrose, polystyrene substitute.
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