CN105449178A - Preparation method for lithium manganese phosphate/graphene/carbon nanocomposite - Google Patents
Preparation method for lithium manganese phosphate/graphene/carbon nanocomposite Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a preparation method for a lithium manganese phosphate/graphene/carbon nanocomposite. The preparation method comprises the specific steps of taking ethylene glycol and deionized water as a reaction medium; adding glucose into the ethylene glycol and performing thermal insulation at a temperature of 130-150 DEG C for 1-5h to online generate an ethylene glycol glucoside surfactant, taking the surfactant as a crystal particle generation inhibitor; dispersing graphene oxide into the surfactant; taking lithium hydroxide, soluble manganese salt and phosphoric acid as the raw materials, and taking deionized water as solvent; regulating and controlling to enable the volume ratio of the ethylene glycol to water to be 3.5:1-1:1.5 to control the boiling point of reaction liquid to be 130-150 DEG C, and performing a backflow reaction for 6-24h to obtain a lithium manganese phosphate/graphene composite material; then performing recombination between the lithium manganese phosphate/graphene composite material and an organic carbon source to obtain the lithium manganese phosphate/graphene/carbon nanocomposite. The synthesized target product obtained in the invention can shorten the transfer distance of lithium ions among solid phases; and in addition, the electronic conductivity among particles is greatly improved due to a conductive network formed by amorphous carbon generated in splitting decomposition of graphene and the organic carbon source.
Description
Technical field
The invention belongs to the synthesis technical field of anode material for lithium-ion batteries, be specifically related to a kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material.
Background technology
LiMnPO
4have and LiFePO
4identical olivine structural, theoretical specific capacity is identical, but its operating voltage is that 4.1V(is relative to Li/Li
+electrode potential), this voltage is just in time positioned at the electrochemical window of existing lithium-ion battery electrolytes system.Therefore, due to higher operating voltage, LiMnPO
4theoretical specific energy can reach nearly 700Wh/kg, compare LiFePO
4exceed about 20%.In addition LiMnPO
4have raw material resources to enrich, price is cheap, environmental friendliness, Stability Analysis of Structures, and the good and fail safe advantages of higher of chemical compatibility, is considered to a kind of power type lithium-ion battery anode material having development prospect.
But LiMnPO
4the electron conduction of material and ionic diffusion coefficient are than LiFePO
4much smaller, thus cause the invertibity of material and high rate performance poor.The people such as Yamada with First Principle to LiMnPO
4electron energy level calculates, and electronics is at LiMnPO
4the energy gap of middle generation transition is 2eV, substantially belongs to insulator.Therefore synthesis can the LiMnPO of reversible discharge and recharge
4very difficult, this is also that this material not yet can realize the main cause of industrialization so far.
Research shows, the nanometer of electrode active material particles and the carbon that covers of nano grain surface are the effective ways improving ionic diffusion coefficient and electron conduction.But due to LiMnPO
4insulating properties itself, to its granular size and dispersed requirement more than LiFePO
4harsh.Be that main ball-milling method is compared with sol-gal process with high temperature solid-phase sintering, hydro-thermal or solvent-thermal method and polyol process, owing to being be main in liquid phase reactor, be more suitable for preparation and the regulation and control of nano particle.But the LiMnPO of hydro thermal method and polyol process synthesis
4particle is mostly nanoscale in some dimensions, and other dimensions remain micron order, such as nanometer rods and nanometer sheet, although diameter or thickness are at 100 ran, length or width often reach several microns.Such as, Y.Z.Dong etc. (JournalofPowerSources2012,215:116-121) report one and prepare LiMnPO at high temperature under high pressure
4the solvent thermal process of nanometer sheet, although thickness is 50 nanometers, the width dimensions of nanometer sheet then reaches 2 microns.Number of patent application is that the patent of invention of 201510097239.X discloses one and prepares LiMnPO
4the method of nanometer rods, spent glycol and aqueous liquid tie up to 180 DEG C of reaction 10h, but reaction needed is carried out in the container of HTHP.Application number is that the patent of invention of 201410562468.X discloses a kind of LiMnPO
4the preparation method of Nano microsphere, to be reunited the microballoon formed by nanometer rods for solvent generates through the reaction of 160-240 DEG C in airtight high-pressure bottle with ethylene glycol and the aqueous solution.Number of patent application be 201410564186.3 patent of invention adopt same system and way to synthesize diameter 200 nanometer, the flower-shaped LiMnPO of micron that nanometer rods that length is 2 microns is assembled
4particle.Application number be 201410413701.8 patent of invention to disclose the hot method of a kind of ethylene glycol solvent be that mineralizer has synthesized and assembles by nanometer rods the major diameter 0.8-2.8 micron formed, the oval ball of minor axis 0.5-1.8 micron at high temperature under high pressure with KOH.These micron particles assembled by nanometer rods, are difficult to carbon-coating is coated on inner nanorod surfaces in follow-up carbon technique of covering, directly affects the electric conductivity of material internal primary particle.Application number is 201410413620.8,201410413442.9 with the patent of invention of 201410413515.4 discloses a kind of method of synthesis of nano particle, but have employed expensive P123 and P127 triblock copolymer in synthesis as template, react in addition and still carry out at high-pressure sealed reactor, need HTHP.Application number be 201410232083.7 patent of invention open a kind of with polyethylene glycol and dimethyl formamide for organic solvent, be that nanometer LiMnPO prepared by surfactant with oleic acid
4the method of particle, the method also needs to carry out in high-pressure hydrothermal reaction kettle.The above micro-nano LiMnPO
4the synthesis major part of particle is all the solvent method with HTHP, and reaction needed is carried out in the container of high pressure-temperature, complicated operation, and cost is high.In recent years, it is found that Graphene has ultra-thin flexible and excellent electric conductivity, it can be used as conductive agent and LiMnPO
4particles dispersed is to improve intergranular conductivity.Such as, the number of applying for a patent be 201410112130.4 patent of invention disclose a kind of method preparing sheet lithium manganese phosphate/graphene composite material, the method adopt be spraying dry assisted with high-temperature sintering method, what synthesize is micron-size spherical particles.Application number be 201310278122.2 patent of invention report and a kind ofly the agraphitic carbon of Graphene and organic carbon source cracking performance is formed conductive network improve LiMnPO
4the conductivity of particle.But the method that the method adopts is the hydro-thermal reaction of HTHP, needs high temperature and pressure.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material, glucose in the method solution and ethylene glycol effect can generating glycol glucoside be the growth that the surfactant led can suppress particle effectively, part glucose in solution and ethylene glycol have reduction, graphene oxide can be reduced into Graphene, and with generate nanometer LiMnPO
4compound is prepared size in any dimension and is no more than the LiMnPO of 150nm
4/ graphene composite material, processes 1-5h in 500-700 DEG C under finally composite material and organic carbon source being blended in inert gas shielding and 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 has excellent electronic conductivity, and the particle of nano-scale substantially reduces lithium ion solid phase transmission distance, achieves LiMnPO
4the synergy of particle nanometer and Graphene and agraphitic carbon conductive network, can substantially improve LiMnPO
4the chemical property of material.
The above-mentioned technical problem of Wei Xie Decision of the present invention adopts following technical scheme, a kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material, it is characterized in that concrete steps are:
(1) glucose to be dissolved in ethylene glycol and at N
2obtain yellow solution A in 130-150 DEG C of insulation 1-5h under protection, wherein the addition of glucose is the corresponding glucose 1-20g of every 100mL ethylene glycol;
(2) graphene oxide is distributed in solution A the solution A obtained containing graphene oxide, by lithium hydroxide, the mol ratio of soluble manganese salt and phosphoric acid is that the ratio of 3:1:1 takes raw material respectively, lithium hydroxide is dissolved in deionized water and prepares lithium hydroxide solution, again lithium hydroxide solution is joined in the solution A containing graphene oxide and form uniform solution B, soluble manganese salt and phosphoric acid are dissolved in obtain solution C in deionized water, solution C is joined forming reactions solution in solution B again, wherein deionized water and step (1) is used to make the volume ratio of spent glycol be that 1:3.5-1.5:1 makes the boiling point control of reaction solution at 130-150 DEG C by regulating,
(3) reaction solution that step (2) obtains is placed in the reaction vessel with reflux, at N
2in 130-150 DEG C of back flow reaction 6-24h under protection, gained sediment washs and obtained nano lithium manganese phosphate of lithium/graphene composite material after vacuumize through centrifugal, deionized water;
(4) under inert gas shielding, 2-6h is incubated in 500-700 DEG C after being mixed with organic carbon source by nano lithium manganese phosphate of lithium/graphene composite material that step (3) obtains; pulverize after cooling and obtain nano lithium manganese phosphate of lithium/graphene/carbon composite material; wherein the consumption of organic carbon source is the 10%-20% of nano lithium manganese phosphate of lithium/graphene composite material quality, and inert gas is the mist of argon gas, nitrogen, argon gas and hydrogen or the mist of nitrogen and hydrogen.
Further restriction, the glucose described in step (1) and glycol reaction generating glycol glucose glycocide surfactant are as the agent of crystal grain Developing restraint.
Further restriction, the soluble manganese salt described in step (2) is manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
Further restriction, the vacuumize condition described in step (3) is 80 DEG C of vacuumize 12h.
Further restriction, the organic carbon source described in step (4) is glucose, sucrose, starch, phenolic resins or polyvinyl alcohol.
Further restriction, in the mist of the inert gas argon gas described in step (4) and hydrogen or the mist of nitrogen and hydrogen, the volumn concentration of hydrogen is 1%-10%.
The present invention compared with prior art has the following advantages:
(1) the present invention adopts normal pressure liquid phase synthesis, and adopt ethylene glycol and water as reaction medium, reaction temperature is lower than 150 DEG C, avoid the harsh conditions that solvent-thermal method needs HTHP, technological operation is simple, and reaction condition is gentle, agents useful for same is cheap, environmental protection;
(2) adopt online synthesizing glycol glucose glycocide surfactant as grain growth inhibitor, not only simple to operate, with low cost, and also the growth that effectively can control crystal grain is less than 150nm in full dimension size;
(3) nano particle generated in the liquid phase is attracted to graphenic surface, and nano particle can be interconnected by the conductive network that Graphene is formed, and increases its conductive capability;
(4) nano lithium manganese phosphate of lithium/graphene/carbon composite material of the present invention's synthesis is not only conducive to shortening the transmission distance of lithium ion in solid phase, and the conductive network that the agraphitic carbon that produces of Graphene and organic carbon source cracking is formed greatly strengthen intergranular electronic conductivity, effectively can improve the chemical property of lithium manganese phosphate, especially high voltage platform property.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the nano lithium manganese phosphate of lithium particle that the embodiment of the present invention 1 obtains;
Fig. 2 is the SEM figure of nano lithium manganese phosphate of lithium/graphene/carbon composite material that the embodiment of the present invention 1 obtains;
Fig. 3 is the grain size distribution of nano lithium manganese phosphate of lithium/graphene/carbon composite material that the embodiment of the present invention 1 obtains;
Fig. 4 is the SEM figure of lithium manganese phosphate/graphene/carbon composite material that comparative example 1 of the present invention obtains;
Fig. 5 is the charge discharge curve of the target product that the embodiment of the present invention 1 obtains with comparative example 1.
Embodiment
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Get 6g glucose to be dissolved in 60mL ethylene glycol and at N
2in 140 DEG C of insulation 2h under protection, make ethylene glycol solution color become faint yellow by colourless, now show in ethylene glycol solution, have glycol polyglucoside class surfactant to generate, finally obtain yellow solution A.Get in 31.4mg graphene oxide ultrasonic disperse to solution A the solution A obtained containing graphene oxide.Get 0.06mol lithium hydroxide (LiOHH
2o) be dissolved in 15mL deionized water, itself and solution A mixing and stirring are obtained solution B.Get 0.02mol manganese sulfate (MnSO
4) and 0.02mol phosphoric acid (H
3pO
4) be dissolved in 15mL deionized water and obtain solution C, solution C is joined forming reactions solution in solution B, at N
2by reaction solution heating reflux reaction 12h under protection, back flow reaction temperature is 139 DEG C.Reaction precipitation thing is centrifugal through 8000r/min, and deionized water washing and 80 DEG C of vacuumize 12h obtain nano lithium manganese phosphate of lithium/graphene composite material.Being mixed with the glucose of nano lithium manganese phosphate of lithium/graphene composite material quality 20% by the nano lithium manganese phosphate of lithium/graphene composite material of gained is placed in tube furnace, under nitrogen protection in 600 DEG C of carbonization 3h, obtains target product after cooling through ball mill grinding.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis
4structure (as shown in Figure 1), the pattern almost spherical of ESEM display-object product, maximum particle diameter be 150nm(as shown in Figure 2), total carbon amounts of covering is 5.0%.
The ratio of nano lithium manganese phosphate of lithium/graphene/carbon composite material, acetylene black and PVDF 85:10:5 is in mass ratio mixed, add a certain amount of NMP and be mixed and made into slurry, slurry is spread evenly across on aluminium foil, in vacuum drying chamber, after 120 DEG C of dry 12h, Kun is pressed into positive plate, using metal lithium sheet as negative pole, microporous polypropylene membrane as barrier film, with 1mol/LLiPF
6/ DEC+DMC+EC (volume ratio 1:1:1), as electrolyte, dresses up CR2016 type button cell in the glove box being full of argon gas.Use LAND battery test system to carry out electric performance test, start-stop voltage to be 3.0-4.5V, 0.05C discharge capacity be 162.2mAh/g(is as shown in Figure 5), and there is good high voltage platform property, more than 3.8V discharge capacity reaches 118mAh/g.
Embodiment 2
Get 8g glucose to be dissolved in 40mL ethylene glycol and at N
2in 130 DEG C of insulation 5h under protection, make ethylene glycol solution color become faint yellow by colourless, now show in ethylene glycol solution, have glycol polyglucoside class surfactant to generate, finally obtain yellow solution A.Get the solution A that 15.7mg graphene oxide ultrasonic disperse obtains containing graphene oxide in solution A.Get 0.06mol lithium hydroxide (LiOHH
2o) be dissolved in 30mL deionized water, itself and solution A mixing and stirring are obtained solution B.Get 0.02mol manganese chloride (MnCl
2) and 0.02mol phosphoric acid (H
3pO
4) be dissolved in 30mL deionized water and obtain solution C, solution C is joined forming reactions solution in solution B, at N
2by reaction solution heating reflux reaction 24h under protection, back flow reaction temperature is 130 DEG C.Reaction precipitation thing is centrifugal through 8000r/min, and deionized water washing and 80 DEG C of vacuumize 12h obtain nano lithium manganese phosphate of lithium/graphene composite material.Being mixed with the sucrose of nano lithium manganese phosphate of lithium/graphene composite material quality 15% by the nano lithium manganese phosphate of lithium/graphene composite material obtained is placed in tube furnace; in 600 DEG C of carbonization 2h under inert gas shielding; wherein inert gas is the mist of nitrogen and hydrogen; the volume fraction of hydrogen is 5%, obtains target product after cooling grinds.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis
4structure, the pattern almost spherical of ESEM display-object product, maximum particle diameter is 140nm, and it is 3.5nm that particle covers carbon thickness, and phosphorus content is 3.5%.Be 159.2mAh/g through electro-chemical test 0.05C discharge capacity, high-voltage discharge platform is excellent, and more than 3.8V discharge capacity reaches 116mAh/g.
Embodiment 3
Get 0.7g glucose to be dissolved in 70mL ethylene glycol and at N
2in 150 DEG C of insulation 1h under protection, make ethylene glycol solution color become faint yellow by colourless, now show in ethylene glycol solution, have glycol polyglucoside class surfactant to generate, finally obtain yellow solution A.Get the solution A that 31.4mg graphene oxide ultrasonic disperse obtains containing graphene oxide in solution A.Get 0.03mol lithium hydroxide (LiOHH
2o) be dissolved in 10mL deionized water, itself and solution A mixing and stirring are obtained solution B.Get 0.01mol manganese nitrate (Mn (NO
3)
2) and 0.01mol phosphoric acid (H
3pO
4) be dissolved in 10mL deionized water and obtain solution C, solution C is joined forming reactions solution in solution B, at N
2by reaction solution heating reflux reaction 6h under protection, back flow reaction temperature is 150 DEG C.Reaction precipitation thing is centrifugal through 8000r/min, and deionized water washing and 80 DEG C of vacuumize 12h obtain nano lithium manganese phosphate of lithium/graphene composite material.Being mixed with the sucrose of nano lithium manganese phosphate of lithium/graphene composite material quality 10% by the nano lithium manganese phosphate of lithium/graphene composite material obtained is placed in tube furnace; in 500 DEG C of carbonization 6h under inert gas shielding; wherein inert gas is the mist of nitrogen and hydrogen; the volumn concentration of hydrogen is 5%, obtains target product after cooling grinds.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis
4structure, the pattern almost spherical of ESEM display-object product, maximum particle diameter is 145nm, and phosphorus content is 2.5%.Be respectively 158.2mAh/g through electro-chemical test 0.05C discharge capacity, high-voltage discharge platform property is excellent, and more than 3.8V discharge capacity reaches 115mAh/g.
Embodiment 4
Get 10g glucose to be dissolved in 50mL ethylene glycol and at N
2in 134 DEG C of insulation 4h under protection, make ethylene glycol solution color become faint yellow by colourless, now show in ethylene glycol solution, have glycol polyglucoside class surfactant to generate, finally obtain yellow solution A.Get the solution A that 188.4mg graphene oxide ultrasonic disperse obtains containing graphene oxide in solution A.Get 0.12mol lithium hydroxide (LiOHH
2o) be dissolved in 25mL deionized water, itself and solution A mixing and stirring are obtained solution B.Get 0.04mol manganese acetate (Mn (CH
3cOO)
2) and 0.04mol phosphoric acid (H
3pO
4) be dissolved in 25mL deionized water and obtain solution C, solution C is joined forming reactions solution in solution B, at N
2by reaction solution heating reflux reaction 12h under protection, back flow reaction temperature is 134 DEG C.Reaction precipitation thing is centrifugal through 8000r/min, and deionized water washing and 80 DEG C of vacuumize 12h obtain nano lithium manganese phosphate of lithium/graphene composite material.Being mixed with the phenolic resins of nano lithium manganese phosphate of lithium/graphene composite material quality 15% by the nano lithium manganese phosphate of lithium/graphene composite material obtained is placed in tube furnace, under nitrogen protection in 700 DEG C of carbonization 2h, obtains target product after cooling grinds.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis
4structure, the pattern almost spherical of ESEM display-object product, maximum particle diameter is 135nm, and phosphorus content is 3.0%.Be 160.1mAh/g through electro-chemical test 0.05C discharge capacity, high voltage platform property is excellent, and more than 3.8V discharge capacity reaches 116mAh/g..
Embodiment 5
Get 6g glucose to be dissolved in 60mL ethylene glycol and at N
2in 140 DEG C of insulation 2h under protection, make ethylene glycol solution color become faint yellow by colourless, now show in ethylene glycol solution, have glycol polyglucoside class surfactant to generate, finally obtain yellow solution A.Get the solution A that 156.7mg graphene oxide ultrasonic disperse obtains containing graphene oxide in solution A.Get 0.06mol lithium hydroxide (LiOHH
2o) be dissolved in 15mL deionized water, itself and solution A mixing and stirring are obtained solution B.Get 0.02mol manganese sulfate (MnSO
4) and 0.02mol phosphoric acid (H
3pO
4) be dissolved in 15mL deionized water and obtain solution C, solution C is joined forming reactions solution in solution B, at N
2by reaction solution heating reflux reaction 12h under protection, back flow reaction temperature is 139 DEG C.Reaction precipitation thing is centrifugal through 8000r/min, and deionized water washing and 80 DEG C of vacuumize 12h obtain nano lithium manganese phosphate of lithium/graphene composite material.Get nano lithium manganese phosphate of lithium/graphene composite material to mix with the glucose of nano lithium manganese phosphate of lithium/graphene composite material quality 20% and be placed in tube furnace, under nitrogen protection in 600 DEG C of carbonization 3h, after cooling, obtain target product through ball mill grinding.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis
4structure, the pattern almost spherical of ESEM display-object product, maximum particle diameter is 150nm, and total carbon amounts of covering is 5.2%.Be 156.1mAh/g through electro-chemical test 0.05C discharge capacity, high voltage platform property is excellent, and more than 3.8V discharge capacity reaches 110mAh/g..
Comparative example 1
Get 0.06mol lithium hydroxide (LiOHH
2o) be dissolved in 15mL deionized water, be directly mixed to form solution B with the 60mL ethylene glycol containing 31.4mg graphene oxide.Get 0.02mol manganese sulfate (MnSO
4) and 0.02mol phosphoric acid (H
3pO
4) be dissolved in 15mL deionized water and obtain solution C, solution C is joined forming reactions solution in solution B, all the other steps are identical with embodiment 1.Being mixed with the glucose of lithium manganese phosphate/graphene composite material quality 20% by gained lithium manganese phosphate/graphene composite material is placed in tube furnace, under nitrogen protection in 600 DEG C of carbonization 3h, obtains target product after cooling through ball mill grinding.Prove that obtained lithium manganese phosphate material contains a small amount of impurity through XRD analysis, ESEM display-object product is micron order aggregate (as shown in Figure 4), and total carbon amounts of covering is 4.6%.Be 153.2mAh/g through electro-chemical test 0.05C discharge capacity, but high voltage platform property is poor, more than 3.8V discharge capacity is 73mAh/g.
Embodiment above describes general principle of the present invention, principal character and advantage; the technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (6)
1. a preparation method for nano lithium manganese phosphate of lithium/graphene/carbon composite material, is characterized in that concrete steps are:
(1) glucose to be dissolved in ethylene glycol and at N
2obtain yellow solution A in 130-150 DEG C of insulation 1-5h under protection, wherein the addition of glucose is the corresponding glucose 1-20g of every 100mL ethylene glycol;
(2) graphene oxide is distributed in solution A the solution A obtained containing graphene oxide, by lithium hydroxide, the mol ratio of soluble manganese salt and phosphoric acid is that the ratio of 3:1:1 takes raw material respectively, lithium hydroxide is dissolved in deionized water and prepares lithium hydroxide solution, again lithium hydroxide solution is joined in the solution A containing graphene oxide and form uniform solution B, soluble manganese salt and phosphoric acid are dissolved in obtain solution C in deionized water, solution C is joined forming reactions solution in solution B again, wherein deionized water and step (1) is used to make the volume ratio of spent glycol be that 1:3.5-1.5:1 makes the boiling point control of reaction solution at 130-150 DEG C by regulating,
(3) reaction solution that step (2) obtains is placed in the reaction vessel with reflux, at N
2in 130-150 DEG C of back flow reaction 6-24h under protection, gained sediment washs and obtained nano lithium manganese phosphate of lithium/graphene composite material after vacuumize through centrifugal, deionized water;
(4) under inert gas shielding, 2-6h is incubated in 500-700 DEG C after being mixed with organic carbon source by nano lithium manganese phosphate of lithium/graphene composite material that step (3) obtains; pulverize after cooling and obtain nano lithium manganese phosphate of lithium/graphene/carbon composite material; wherein the consumption of organic carbon source is the 10%-20% of nano lithium manganese phosphate of lithium/graphene composite material quality, and inert gas is the mist of argon gas, nitrogen, argon gas and hydrogen or the mist of nitrogen and hydrogen.
2. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, is characterized in that: the glucose described in step (1) and glycol reaction generating glycol glucose glycocide surfactant are as the agent of crystal grain Developing restraint.
3. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, is characterized in that: the soluble manganese salt described in step (2) is 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, is characterized in that: the vacuumize condition described in step (3) is 80 DEG C of vacuumize 12h.
5. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, is characterized in that: the organic carbon source described in step (4) is glucose, sucrose, starch, phenolic resins or polyvinyl alcohol.
6. the preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material according to claim 1, is characterized in that: in the mist of the inert gas argon gas described in step (4) and hydrogen or the mist of nitrogen and hydrogen, the volumn concentration of hydrogen is 1%-10%.
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| CN112652768A (en) * | 2020-10-23 | 2021-04-13 | 有研工程技术研究院有限公司 | Preparation method of lithium manganese phosphate-graphene composite material, lithium manganese phosphate-graphene composite material and application |
| CN112652768B (en) * | 2020-10-23 | 2022-05-20 | 有研工程技术研究院有限公司 | Preparation method of lithium manganese phosphate-graphene composite material, lithium manganese phosphate-graphene composite material and application |
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