CN105449178B - A kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material - Google Patents
A kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material, concretely comprise the following steps：Reaction medium is used as using ethylene glycol and deionized water, glucose is added first in ethylene glycol and generates glycol polyglucoside class surfactant online as crystal grain formation inhibitor in 130 150 DEG C of 1 5h of insulation, graphene oxide is distributed in above-mentioned surfactant, using lithium hydroxide, soluble manganese salt and phosphoric acid as raw material, it is 3.5 by the volume ratio regulated and controled using ethylene glycol and water using deionized water as solvent:1‑1:1.5 cause the boiling point control of reaction solution at 130 150 DEG C, and nano lithium manganese phosphate of lithium/graphene composite material is made in the 24h of back flow reaction 6, then is combined obtained nano lithium manganese phosphate of lithium/graphene/carbon composite material with organic carbon source.The target product that the present invention is synthesized not only contributes to shorten transmission distance of the lithium ion in solid phase, and the conductive network that graphene cracks the agraphitic carbon produced formation with organic carbon source greatly strengthen intergranular electronic conductivity.
Description
Technical field
The invention belongs to the synthesis technical field of anode material for lithium-ion batteries, and in particular to and a kind of nano lithium manganese phosphate of lithium/
The preparation method of graphene/carbon composite material.
Background technology
LiMnPO4Have and LiFePO4Identical olivine structural, theoretical specific capacity is identical, but its operating voltage is
4.1V（Relative to Li/Li+Electrode potential）, the voltage is placed exactly in the electrochemical window of existing lithium-ion battery electrolytes system
Mouthful.Therefore, because higher operating voltage, LiMnPO4Theoretical specific energy can reach nearly 700Wh/kg, compare LiFePO4It is higher by
About 20%.In addition LiMnPO4Abundant with raw material resources, price is cheap, environment-friendly, Stability Analysis of Structures, and chemical compatibility is good and pacifies
A kind of the advantages of property is high entirely, it is considered to be power type lithium-ion battery anode material of great development prospect.
But LiMnPO4The electron conduction and ionic diffusion coefficient of material are than LiFePO4It is much smaller, so as to cause material
The invertibity and high rate performance of material are poor.Yamada et al. is with First Principle to LiMnPO4Electron energy level is calculated, electronics
In LiMnPO4The middle energy gap for occurring transition is 2eV, substantially belongs to insulator.Therefore the LiMnPO of reversible discharge and recharge is capable of in synthesis4
It is extremely difficult, this be also so far the material can not yet realize the main cause of industrialization.
Research shows that the nanosizing of electrode active material particles and the carbon that covers of nano grain surface are to improve ion diffusion
The effective way of coefficient and electron conduction.But it is due to LiMnPO4The insulating properties of itself, to its granular size and dispersiveness
It is required that more than LiFePO4It is harsh.Compared with ball-milling method and sol-gal process based on high temperature solid-phase sintering, hydro-thermal or solvent-thermal method
And polyol process, due to being based on the liquid phase reactor, to be more suitable for the preparation and regulation and control of nano particle.But hydro-thermal method and polyalcohol
The LiMnPO of method synthesis4Particle is nanoscale mostly in some dimension, and other dimensions are still micron order, such as nanometer
Rod and nanometer sheet, although diameter or thickness often reach a few micrometers in 100 rans, length or width.For example, Y.Z.
Dong etc.（Journal of Power Sources 2012,215：116-121）One kind is reported to prepare at high temperature under high pressure
LiMnPO4The solvent thermal process of nanometer sheet, although thickness is 50 nanometers, but the width dimensions of nanometer sheet then reach 2 microns.Specially
Sharp Application No. 201510097239.X patent of invention discloses one kind and prepares LiMnPO4The method of nanometer rods, spent glycol
180 DEG C of reaction 10h are tied up to aqueous liquid, but reaction needs to carry out in the container of HTHP.Application No.
201410562468.X patent of invention disclose a kind of LiMnPO4The preparation method of nanoparticle, with ethylene glycol and the aqueous solution
For solvent the microballoon reunited by nanometer rods and constituted is generated in closed high-pressure bottle through 160-240 DEG C of reaction.Patent Shen
Number 200 nanometers of diameter please be synthesized using same system and method for 201410564186.3 patent of invention, length 2 is micro-
The flower-shaped LiMnPO of micron of the nanometer rods aggregation of rice4Particle.The patent of invention of Application No. 201410413701.8 is disclosed
A kind of hot method of ethylene glycol solvent has at high temperature under high pressure synthesized by mineralizer of KOH assembles the major diameter constituted by nanometer rods
0.8-2.8 microns, the elliptical shape ball that 0.5-1.8 microns of minor axis.These micron particles assembled by nanometer rods, follow-up
It is difficult the nanorod surfaces that carbon-coating is coated on to inside to cover carbon technique, directly affects the electric conductivity of material internal primary particle
Energy.The patent of invention of Application No. 201410413620.8,201410413442.9 and 201410413515.4 discloses one kind
The method for synthesizing nano particle, but P123 the and P127 triblock copolymers of costliness are employed in synthesis as template, separately
Outer reaction is still carried out, it is necessary to HTHP in high-pressure sealed reactor.The patent of invention of Application No. 201410232083.7
Open one kind prepares nanometer LiMnPO by surfactant of oleic acid using polyethylene glycol and dimethylformamide as organic solvent4
The method of particle, this method is also required to carry out in high-pressure hydrothermal reaction kettle.Micro-nano LiMnPO described above4The synthesis of particle
Most of is all the solvent method with HTHP, and reaction needs to carry out in the container of high pressure-temperature, and complex operation, cost is high.
In recent years, it has been found that graphene has ultra-thin flexible and excellent electric conductivity, as conductive agent and LiMnPO4Particle
It is combined to improve intergranular electric conductivity.For example, the number of applying for a patent discloses one kind for 201410112130.4 patent of invention
The method for preparing sheet lithium manganese phosphate/graphene composite material, this method uses spray drying assisted with high-temperature sintering method,
What is synthesized is micron-size spherical particles.The patent of invention of Application No. 201310278122.2 report it is a kind of by graphene and
The agraphitic carbon formation conductive network of organic carbon source cracking performance improves LiMnPO4The electric conductivity of particle.But this method is used
Method be the hydro-thermal reaction of HTHP, it is necessary to high temperature and pressure.
The content of the invention
Present invention solves the technical problem that there is provided a kind of preparation of nano lithium manganese phosphate of lithium/graphene/carbon composite material
Glucose in method, this method solution, which acts on the surfactant that can be generated based on glycol polyglucoside with ethylene glycol, to be had
The part glucose and ethylene glycol that effect ground suppresses in the growth of particle, solution have reduction, can reduce graphene oxide
Into graphene, and with the nanometer LiMnPO of generation4It is compound to prepare the LiMnPO that the size in any dimension is no more than 150nm4/
Composite and organic carbon source, are finally blended under inert gas shielding and handle 1- in 500-700 DEG C by graphene composite material
5h obtains target product.This nano lithium manganese phosphate of lithium/graphene/carbon composite material is used as anode material for lithium-ion batteries, not only
Particle with excellent electronic conductivity, and nano-scale substantially reduces lithium ion solid phase transmission distance, realizes
LiMnPO4The synergy of particle nanosizing and graphene and agraphitic carbon conductive network, can substantially improve LiMnPO4Material
The chemical property of material.
Wei Xie Decision above-mentioned technical problems of the present invention adopt the following technical scheme that a kind of nano lithium manganese phosphate of lithium/graphene/carbon is multiple
The preparation method of condensation material, it is characterised in that concretely comprise the following steps：
（1）Glucose is dissolved in ethylene glycol and in N21-5h is incubated in 130-150 DEG C yellow solution is made under protection
A, wherein glucose addition are per 100mL ethylene glycol correspondence glucose 1-20g；
（2）Graphene oxide is distributed to the solution A containing graphene oxide is obtained in solution A, by lithium hydroxide, solvable
Property manganese salt and phosphoric acid mol ratio be 3:1:1 ratio weighs raw material respectively, and lithium hydroxide is dissolved in deionized water and matches somebody with somebody hydrogen manufacturing
Lithia solution, then lithium hydroxide solution is added in the solution A containing graphene oxide forms uniform solution B, can
Dissolubility manganese salt and phosphoric acid, which are dissolved in deionized water, prepares solution C, then solution C is added in solution B forms reaction solution, wherein
Deionized water and step are used by adjusting（1）The use of the volume ratio of ethylene glycol is 1:3.5-1.5:1 causes the boiling of reaction solution
Point control is at 130-150 DEG C；
（3）By step（2）Obtained reaction solution is placed in the reaction vessel with reflux, in N2Under protection in
Nanometer phosphoric acid is made after washing and be dried in vacuo through centrifugation, deionized water in 130-150 DEG C of back flow reaction 6-24h, gained sediment
Manganese lithium/graphene composite material；
（4）By step（3）Obtained nano lithium manganese phosphate of lithium/graphene composite material mixed with organic carbon source after in indifferent gas
2-6h is incubated in 500-700 DEG C under body protection, is crushed after cooling and obtains nano lithium manganese phosphate of lithium/graphene/carbon composite material, wherein
The consumption of organic carbon source be nano lithium manganese phosphate of lithium/graphene composite material quality 10%-20%, inert gas be argon gas, nitrogen,
The mixed gas or nitrogen and the mixed gas of hydrogen of argon gas and hydrogen.
Further limit, step（1）Described in glucose and glycol reaction generation glycol polyglucoside class surface
Activating agent suppresses growth stimulator as crystal grain.
Further limit, step（2）Described in soluble manganese salt be manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
Further limit, step（3）Described in vacuum drying condition for 80 DEG C vacuum drying 12h.
Further limit, step（4）Described in organic carbon source be glucose, sucrose, starch, phenolic resin or polyethylene
Alcohol.
Further limit, step（4）Described in inert gas argon gas and hydrogen mixed gas or nitrogen and hydrogen
The volumn concentration of hydrogen is 1%-10% in mixed gas.
The present invention has advantages below compared with prior art：
（1）The present invention uses normal pressure liquid phase synthesis, and using ethylene glycol and water as reaction medium, reaction temperature is less than 150
DEG C, it is to avoid solvent-thermal method needs the harsh conditions of HTHP, and technological operation is simple, and reaction condition is gentle, agents useful for same valency
Lattice are cheap, environmental protection；
（2）Using online synthesizing glycol glucose glycocide surfactant as grain growth inhibitor, not only operate
Simply, it is with low cost, and being grown in for crystal grain can be efficiently controlled tie up entirely smaller in dimension than 150nm；
（3）The nano particle generated in the liquid phase is attracted to graphenic surface, and the conductive network of graphene formation can be by
Nano particle is connected with each other, and increases its conductive capability；
（4）Nano lithium manganese phosphate of lithium/graphene/carbon composite material that the present invention is synthesized not only contributes to shorten lithium ion solid
The transmission distance of phase, and graphene and organic carbon source crack the conductive network of the agraphitic carbon formation produced and greatly strengthen
The electronic conductivity of intergranular, can be effectively improved the chemical property of lithium manganese phosphate, especially high voltage platform property.
Brief description of the drawings
Fig. 1 is the XRD spectrum of nano lithium manganese phosphate of lithium particle made from the embodiment of the present invention 1；
Fig. 2 is the SEM figures of nano lithium manganese phosphate of lithium/graphene/carbon composite material made from the embodiment of the present invention 1；
Fig. 3 is the grain size distribution of nano lithium manganese phosphate of lithium/graphene/carbon composite material made from the embodiment of the present invention 1；
Fig. 4 is the SEM figures of lithium manganese phosphate/graphene/carbon composite material made from comparative example 1 of the present invention；
Fig. 5 is the charge discharge curve of the embodiment of the present invention 1 and target product made from comparative example 1.
Embodiment
The above to the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
6g glucose is taken to be dissolved in 60mL ethylene glycol and in N22h is incubated in 140 DEG C so that ethylene glycol solution face under protection
Color becomes faint yellow by colourless, now shows there is the generation of glycol polyglucoside class surfactant in ethylene glycol solution, finally
Obtain yellow solution A.31.4mg graphene oxide ultrasonic disperses are taken to obtain the solution A containing graphene oxide into solution A.
Take 0.06mol lithium hydroxides（LiOH·H2O）It is dissolved in 15mL deionized waters, itself and solution A is mixed evenly and obtain molten
Liquid B.Take 0.02mol manganese sulfates（MnSO4）With 0.02 mol phosphoric acid（H3PO4）It is dissolved in 15mL deionized waters and obtains solution C, will
Solution C, which is added in solution B, forms reaction solution, in N2By reaction solution heating reflux reaction 12h, back flow reaction temperature under protection
Spend for 139 DEG C.Reaction precipitate is centrifuged through 8000 r/min, and deionized water washing and 80 DEG C of vacuum drying 12h obtain a nanometer phosphorus
Sour manganese lithium/graphene composite material.By nano lithium manganese phosphate of lithium/graphene composite material of gained and nano lithium manganese phosphate of lithium/graphite
It is placed in after the glucose mixing of alkene composite quality 20% in tube furnace, be carbonized 3h in 600 DEG C under nitrogen protection, after cooling
Target product is obtained through ball mill grinding.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis4Structure
（As shown in Figure 1）, the pattern almost spherical of ESEM display target product, maximum particle diameter is 150nm（As shown in Figure 2）, always
Cover carbon amounts for 5.0%.
By nano lithium manganese phosphate of lithium/graphene/carbon composite material, acetylene black and PVDF in mass ratio 85:10:5 ratio is mixed
Close uniform, add a certain amount of NMP and be mixed and made into slurry, slurry is spread evenly across on aluminium foil, 120 DEG C in vacuum drying chamber
Dry Kun after 12h and be pressed into positive plate, using metal lithium sheet as negative pole, microporous polypropylene membrane is as barrier film, with 1mol/L
LiPF6/ DEC+DMC+EC (volume ratios 1:1:1) as electrolyte, CR2016 type buttons are dressed up in the glove box full of argon gas
Battery.Electric performance test is carried out using LAND battery test systems, start-stop voltage is 3.0-4.5V, and 0.05C discharge capacities are
162.2mAh/g（As shown in Figure 5）, and with good high voltage platform property, more than 3.8V discharge capacities reach 118mAh/
g。
Embodiment 2
8g glucose is taken to be dissolved in 40mL ethylene glycol and in N25h is incubated in 130 DEG C so that ethylene glycol solution face under protection
Color becomes faint yellow by colourless, now shows there is the generation of glycol polyglucoside class surfactant in ethylene glycol solution, finally
Obtain yellow solution A.15.7mg graphene oxide ultrasonic disperses are taken to obtain the solution A containing graphene oxide in solution A.
Take 0.06mol lithium hydroxides（LiOH·H2O）It is dissolved in 30mL deionized waters, itself and solution A is mixed evenly and obtain molten
Liquid B.Take 0.02mol manganese chlorides（MnCl2）With 0.02mol phosphoric acid（H3PO4）It is dissolved in 30mL deionized waters and obtains solution C, will be molten
Liquid C, which is added in solution B, forms reaction solution, in N2By reaction solution heating reflux reaction 24h, back flow reaction temperature under protection
For 130 DEG C.Reaction precipitate is centrifuged through 8000r/min, and deionized water washing and 80 DEG C of vacuum drying 12h obtain nano manganese phosphate
Lithium/graphene composite material.Obtained nano lithium manganese phosphate of lithium/graphene composite material and nano lithium manganese phosphate of lithium/graphene is multiple
It is placed in after the sucrose mixing of condensation material quality 15% in tube furnace, be carbonized 2h, wherein inertia under inert gas shielding in 600 DEG C
Gas is the mixed gas of nitrogen and hydrogen, and the volume fraction of hydrogen is 5%, and cooling obtains target product after grinding.Through
XRD analysis prove that it is pure phase olivine LiMnPO that lithium manganese phosphate material, which is made,4Structure, the pattern of ESEM display target product
Almost spherical, maximum particle diameter is 140nm, and particle covers carbon thickness for 3.5nm, and phosphorus content is 3.5%.Put through electro-chemical test 0.05C
Capacitance is 159.2mAh/g, and high-voltage discharge platform is excellent, and more than 3.8V discharge capacities reach 116mAh/g.
Embodiment 3
0.7g glucose is taken to be dissolved in 70mL ethylene glycol and in N21h is incubated in 150 DEG C so that ethylene glycol solution under protection
Color becomes faint yellow by colourless, now shows there is the generation of glycol polyglucoside class surfactant in ethylene glycol solution, most
Yellow solution A is obtained eventually.31.4mg graphene oxide ultrasonic disperses are taken to obtain the solution containing graphene oxide in solution A
A.Take 0.03mol lithium hydroxides（LiOH·H2O）It is dissolved in 10mL deionized waters, it is mixed evenly with solution A and obtained
Solution B.Take 0.01mol manganese nitrates（Mn(NO3)2）With 0.01mol phosphoric acid（H3PO4）It is dissolved in 10mL deionized waters and obtains solution
C, solution C is added in solution B and forms reaction solution, in N2By reaction solution heating reflux reaction 6h under protection, backflow is anti-
It is 150 DEG C to answer temperature.Reaction precipitate is centrifuged through 8000r/min, and deionized water washing and 80 DEG C of vacuum drying 12h obtain nanometer
Lithium manganese phosphate/graphene composite material.By obtained nano lithium manganese phosphate of lithium/graphene composite material and nano lithium manganese phosphate of lithium/stone
It is placed in after the sucrose mixing of black alkene composite quality 10% in tube furnace, be carbonized 6h under inert gas shielding in 500 DEG C, its
Middle inert gas is the mixed gas of nitrogen and hydrogen, and the volumn concentration of hydrogen is 5%, and cooling obtains mesh after grinding
Mark product.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis4Structure, ESEM shows mesh
The pattern almost spherical of product is marked, maximum particle diameter is 145nm, and phosphorus content is 2.5%.Through electro-chemical test 0.05C discharge capacities point
Not Wei 158.2mAh/g, high-voltage discharge platform property is excellent, and more than 3.8V discharge capacities reach 115mAh/g.
Embodiment 4
10g glucose is taken to be dissolved in 50mL ethylene glycol and in N24h is incubated in 134 DEG C so that ethylene glycol solution face under protection
Color becomes faint yellow by colourless, now shows there is the generation of glycol polyglucoside class surfactant in ethylene glycol solution, finally
Obtain yellow solution A.188.4mg graphene oxide ultrasonic disperses are taken to obtain the solution containing graphene oxide in solution A
A.Take 0.12mol lithium hydroxides（LiOH·H2O）It is dissolved in 25mL deionized waters, it is mixed evenly with solution A and obtained
Solution B.Take 0.04mol manganese acetates（Mn(CH3COO)2）With 0.04mol phosphoric acid（H3PO4）It is dissolved in 25mL deionized waters and obtains molten
Liquid C, solution C is added in solution B and forms reaction solution, in N2By reaction solution heating reflux reaction 12h under protection, backflow
Reaction temperature is 134 DEG C.Reaction precipitate is centrifuged through 8000r/min, and deionized water washing and 80 DEG C of vacuum drying 12h are received
Rice lithium manganese phosphate/graphene composite material.By obtained nano lithium manganese phosphate of lithium/graphene composite material and nano lithium manganese phosphate of lithium/
It is placed in after the phenolic resin mixing of graphene composite material quality 15% in tube furnace, be carbonized 2h in 700 DEG C under nitrogen protection,
Cooling obtains target product after grinding.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis4
Structure, the pattern almost spherical of ESEM display target product, maximum particle diameter is 135nm, and phosphorus content is 3.0%.Through electrochemistry
It is 160.1mAh/g to test 0.05C discharge capacities, and high voltage platform property is excellent, and more than 3.8V discharge capacities reach 116mAh/
g.。
Embodiment 5
6g glucose is taken to be dissolved in 60mL ethylene glycol and in N22h is incubated in 140 DEG C so that ethylene glycol solution face under protection
Color becomes faint yellow by colourless, now shows there is the generation of glycol polyglucoside class surfactant in ethylene glycol solution, finally
Obtain yellow solution A.156.7mg graphene oxide ultrasonic disperses are taken to obtain the solution containing graphene oxide in solution A
A.Take 0.06mol lithium hydroxides（LiOH·H2O）It is dissolved in 15mL deionized waters, it is mixed evenly with solution A and obtained
Solution B.Take 0.02mol manganese sulfates（MnSO4）With 0.02mol phosphoric acid（H3PO4）It is dissolved in 15mL deionized waters and obtains solution C, will
Solution C, which is added in solution B, forms reaction solution, in N2By reaction solution heating reflux reaction 12h, back flow reaction temperature under protection
Spend for 139 DEG C.Reaction precipitate is centrifuged through 8000r/min, and deionized water washing and 80 DEG C of vacuum drying 12h obtain a nanometer phosphoric acid
Manganese lithium/graphene composite material.Take nano lithium manganese phosphate of lithium/graphene composite material and nano lithium manganese phosphate of lithium/graphene composite wood
It is placed in after the glucose mixing of material quality 20% in tube furnace, be carbonized 3h in 600 DEG C under nitrogen protection, through ball milling powder after cooling
It is broken to obtain target product.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis4Structure, scanning electricity
The pattern almost spherical of mirror display target product, maximum particle diameter is 150nm, and total carbon amounts of covering is 5.2%.Through electro-chemical test
0.05C discharge capacities are 156.1mAh/g, and high voltage platform property is excellent, and more than 3.8V discharge capacities reach 110mAh/g..
Comparative example 1
Take 0.06mol lithium hydroxides（LiOH·H2O）It is dissolved in 15mL deionized waters, directly with aoxidizing stone containing 31.4mg
The 60mL ethylene glycol of black alkene is mixed to form solution B.Take 0.02mol manganese sulfates（MnSO4）With 0.02mol phosphoric acid（H3PO4）It is dissolved in
Solution C is obtained in 15mL deionized waters, solution C is added in solution B and forms reaction solution, remaining step and the phase of embodiment 1
Together.Gained lithium manganese phosphate/graphene composite material is mixed with the glucose of lithium manganese phosphate/graphene composite material quality 20%
After be placed in tube furnace, under nitrogen protection in 600 DEG C be carbonized 3h, obtain target product through ball mill grinding after cooling.Through XRD points
Analysis proves that obtained lithium manganese phosphate material contains a small amount of impurity, and ESEM display target product is micron-sized aggregate（Such as Fig. 4
It is shown）, total carbon amounts of covering is 4.6%.It is 153.2mAh/g through electro-chemical test 0.05C discharge capacities, but high voltage platform
Can be poor, more than 3.8V discharge capacities are 73mAh/g.
Embodiment above describes general principle, principal character and the advantage of the present invention, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (6)
1. a kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material, it is characterised in that concretely comprise the following steps：
（1）Glucose is dissolved in ethylene glycol and in N21-5h is incubated in 130-150 DEG C yellow solution A is made under protection, wherein
The addition of glucose is per 100mL ethylene glycol correspondence glucose 1-20g；
（2）Graphene oxide is distributed to the solution A containing graphene oxide is obtained in solution A, wherein graphene oxide with it is molten
The charge ratio of ethylene glycol is 31.4mg in liquid A:60mL、15.7mg:40mL、31.4mg:70mL、188.4mg:50mL or
156.7mg:60mL, the mol ratio by lithium hydroxide, soluble manganese salt and phosphoric acid is 3:1:1 ratio weighs raw material respectively, will
Lithium hydroxide, which is dissolved in deionized water, prepares lithium hydroxide solution, then lithium hydroxide solution is added to containing graphene oxide
Uniform solution B is formed in solution A, soluble manganese salt and phosphoric acid are dissolved in deionized water and prepare solution C, then solution C is added
Enter and reaction solution is formed into solution B, wherein using deionized water and step by adjusting（1）It is using the volume ratio of ethylene glycol
1:3.5-1.5:1 causes the boiling point control of reaction solution at 130-150 DEG C；
（3）By step（2）Obtained reaction solution is placed in the reaction vessel with reflux, in N2In 130-150 under protection
DEG C back flow reaction 6-24h, gained sediment through centrifugation, deionized water wash and vacuum drying after nano lithium manganese phosphate of lithium/stone is made
Black alkene composite；
（4）By step（3）Obtained nano lithium manganese phosphate of lithium/graphene composite material is protected after being mixed with organic carbon source in inert gas
2-6h is incubated in 500-700 DEG C under shield, is crushed after cooling and obtains nano lithium manganese phosphate of lithium/graphene/carbon composite material, wherein organic
The consumption of carbon source is the 10%-20% of nano lithium manganese phosphate of lithium/graphene composite material quality, and inert gas is argon gas, nitrogen, argon gas
With the mixed gas or nitrogen and the mixed gas of hydrogen of hydrogen.
2. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, it is characterised in that：
Step（1）Described in glucose and glycol reaction generation glycol polyglucoside class surfactant be used as crystal grain to suppress to give birth to
Long agent.
3. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, it is characterised in that：
Step（2）Described in soluble manganese salt be manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
4. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, it is characterised in that：
Step（3）Described in vacuum drying condition for 80 DEG C vacuum drying 12h.
5. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, it is characterised in that：
Step（4）Described in organic carbon source be glucose, sucrose, starch, phenolic resin or polyvinyl alcohol.
6. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, it is characterised in that：
Step（4）Described in inert gas argon gas and the mixed gas or nitrogen of hydrogen and the mixed gas of hydrogen in hydrogen volume
Percentage composition is 1%-10%.
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