CN105514376A - Method for preparing nano lithium manganese phosphate/graphene composite - Google Patents

Method for preparing nano lithium manganese phosphate/graphene composite Download PDF

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CN105514376A
CN105514376A CN201510928559.5A CN201510928559A CN105514376A CN 105514376 A CN105514376 A CN 105514376A CN 201510928559 A CN201510928559 A CN 201510928559A CN 105514376 A CN105514376 A CN 105514376A
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solution
lithium
ethylene glycol
deionized water
reaction
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CN105514376B (en
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常焜
汤宏伟
谢峥峥
李苞
上官恩波
常照荣
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Henan Normal University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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

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Abstract

The invention discloses a method for preparing a nano lithium manganese phosphate/graphene composite. The method comprises the specific steps that ethylene glycol and deionized water are adopted as a reaction medium, glucose is firstly added to ethylene glycol, the temperature is kept at 130 DEG C to 150 DEG C for 1 h to 5 h, an ethylene glycol glucoside surface active agent is online generated and serves as a crystalline grain generation inhibitor, graphene oxide is dispersed into the surface active agent, lithium hydroxide, soluble manganese salt and phosphoric acid are adopted as raw materials, deionized water is adopted as a solvent, the volume ratio of ethylene glycol to the water is regulated and controlled to range from 3.5:1 to 1:1.5, the boiling point of the reaction solution is controlled to be from 130 DEG C to 150 DEG C, a reflux reaction is carried out for 6 h to 24 h, and the nano lithium manganese phosphate/graphene composite is prepared. The synthesized nano lithium manganese phosphate/graphene composite is beneficial to reducing the transfer distance of lithium ions in a solid phase, compounded graphene has better conductivity, and therefore the diffusion rate of the lithium ions in particles is greatly increased, and the electronic conductivity among the particles is greatly enhanced.

Description

A kind of preparation method of nano lithium manganese phosphate of lithium/graphene composite material
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 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.
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 composite material, the method utilizes the part glucose in solution and ethylene glycol to have reduction, graphene oxide can be reduced into Graphene, and prepare with the nano lithium manganese phosphate of lithium compound generated lithium manganese phosphate/graphene composite material that size in any dimension is no more than 150nm, this nano lithium manganese phosphate of lithium/graphene composite material can be used as anode material for lithium-ion batteries.
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 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.
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.
The present invention compared with prior art has the following advantages:
(1) the normal pressure liquid phase one-step that the present invention adopts synthesizes pure phase nanometer lithium manganese phosphate/graphene composite material, 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, and follow-up high temperature purification treatment, 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 lithium manganese phosphate of lithium/graphene composite material of the present invention's synthesis is conducive to shortening the transmission distance of lithium ion in solid phase, the Graphene of compound has good conductivity, thus greatly strengthen the diffusion rate of granule interior lithium ion and intergranular electronic conductivity.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the full dimension nano lithium manganese phosphate of lithium particle that the embodiment of the present invention 1 obtains;
Fig. 2 is the XRD collection of illustrative plates of the lithium manganese phosphate particle that comparative example 1 of the present invention obtains;
Fig. 3 is the SEM figure of nano lithium manganese phosphate of lithium/graphene composite material that the embodiment of the present invention 1 obtains;
Fig. 4 is the grain size distribution of nano lithium manganese phosphate of lithium/graphene composite material that the embodiment of the present invention 1 obtains;
Fig. 5 is the laser Raman spectroscopy figure 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 target product.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis 4structure (as shown in Figure 1), the content of Graphene is 0.5%, the pattern almost spherical (as shown in Figure 3) of ESEM display-object product, maximum particle diameter 150nm(is as shown in Figure 4), laser Raman spectroscopy shows Graphene characteristic peak and there is (as shown in Figure 5).
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 target product.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis 4structure, the content of Graphene is 0.25%, the pattern almost spherical of ESEM display-object product, maximum particle diameter 140nm, and laser Raman spectroscopy shows Graphene characteristic peak to be existed.
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 target product.Prove that obtained lithium manganese phosphate is pure phase olivine LiMnPO through XRD analysis 4structure, the content of Graphene is 1%, the pattern almost spherical of ESEM display-object product, and maximum particle diameter is 145nm, laser Raman spectroscopy shows Graphene characteristic peak to be existed.
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 target product.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 130nm, and laser Raman spectroscopy shows Graphene characteristic peak.
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 target product.Prove that obtained lithium manganese phosphate material is pure phase olivine LiMnPO through XRD analysis 4structure, the content of Graphene is 2.5%, the pattern almost spherical of ESEM display-object product, maximum particle diameter 135nm.
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.According to the XRD collection of illustrative plates of Fig. 2 known comparative example 1 gained sample except containing except the characteristic peak of lithium manganese phosphate, have also appeared some dephasign peaks.
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 (4)

1. a preparation method for nano lithium manganese phosphate of lithium/graphene 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.
2. full Wei Na meter LiMnPO according to claim 1 4the preparation method of particle, 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. full Wei Na meter LiMnPO according to claim 1 4the preparation method of particle, is characterized in that: the soluble manganese salt described in step (2) is manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
4. full Wei Na meter LiMnPO according to claim 1 4the preparation method of particle, is characterized in that: the vacuumize condition described in step (3) is 80 DEG C of vacuumize 12h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110054167A (en) * 2019-03-25 2019-07-26 河南师范大学 A method of preparing manganese phosphate lithium nanosheet in aqueous phase system
CN110071269A (en) * 2019-03-25 2019-07-30 河南师范大学 A method of preparing lithium manganese phosphate/graphene nanometer sheet in aqueous phase system

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102956887A (en) * 2012-11-14 2013-03-06 佛山市德方纳米科技有限公司 Preparation method of nano-grade lithium manganese phosphate anode material
CN103199247A (en) * 2013-03-27 2013-07-10 中南大学 Preparation method of composite positive material with multi-level conductive network of lithium ion battery
CN103346319A (en) * 2013-07-04 2013-10-09 河北工业大学 Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102956887A (en) * 2012-11-14 2013-03-06 佛山市德方纳米科技有限公司 Preparation method of nano-grade lithium manganese phosphate anode material
CN103199247A (en) * 2013-03-27 2013-07-10 中南大学 Preparation method of composite positive material with multi-level conductive network of lithium ion battery
CN103346319A (en) * 2013-07-04 2013-10-09 河北工业大学 Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110054167A (en) * 2019-03-25 2019-07-26 河南师范大学 A method of preparing manganese phosphate lithium nanosheet in aqueous phase system
CN110071269A (en) * 2019-03-25 2019-07-30 河南师范大学 A method of preparing lithium manganese phosphate/graphene nanometer sheet in aqueous phase system
CN110071269B (en) * 2019-03-25 2021-12-24 河南师范大学 Method for preparing lithium manganese phosphate/graphene nanosheet in aqueous phase system
CN110054167B (en) * 2019-03-25 2022-01-25 河南师范大学 Method for preparing lithium manganese phosphate nanosheets in aqueous phase system

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