CN106684368B - Graphene compound phosphoric acid manganese lithium material and preparation method thereof - Google Patents
Graphene compound phosphoric acid manganese lithium material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- ZEEDCGIEVPGBCZ-UHFFFAOYSA-N [Li].[Mn].P(O)(O)(O)=O Chemical compound [Li].[Mn].P(O)(O)(O)=O ZEEDCGIEVPGBCZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 51
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 25
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 15
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 15
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 12
- 238000013019 agitation Methods 0.000 claims abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002604 ultrasonography Methods 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 230000035484 reaction time Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 5
- 239000008118 PEG 6000 Substances 0.000 claims description 4
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 13
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 description 4
- -1 oxygen Graphite alkene Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/58—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of graphene compound phosphoric acid manganese lithium material and preparation method thereof, is related to field of lithium ion battery anode.A kind of preparation method of graphene compound phosphoric acid manganese lithium material, comprising: lithium hydroxide is dissolved in the mixed solvent, sequentially adds manganese sulfate solution, graphene oxide solution obtains the first solution；Under conditions of ultrasound is with stirring, heat preservation, phosphoric acid solution is added into the first solution several times and obtains mixed solution；After carrying out magnetic agitation to mixed solution, mixed solution is transferred to progress first time hydro-thermal reaction in reaction kettle, is cooled to room temperature after reaction, continues heating and carries out second of hydro-thermal reaction, obtain solid precursor；Solid precursor is mixed with glucose, the heating and calcining in the atmosphere of inert gas.The preparation method improves the electrical property of product, and process flow is simple, can be mass.A kind of graphene compound phosphoric acid manganese lithium material, is prepared by above-mentioned preparation method, and product electrical property is high.
Description
Technical field
The present invention relates to field of lithium ion battery anode, and in particular to a kind of graphene compound phosphoric acid manganese lithium material
And preparation method thereof.
Background technique
With the rapid exhausted of fossil energy and due to using environmental pollution caused by fossil energy to get worse, such as
What exploitation is selected using new energy, saving using the Major Strategic that fossil energy has become country.As energy-conserving and emission-cutting technology
Representative, electric energy at emphasis developing direction.
Lithium ion battery is a kind of rechargeable battery, has obtained relatively broad application at present.Lithium ion battery one
As by anode, cathode, diaphragm, electrolyte and battery case etc. part form, wherein the cost of positive electrode accounts for battery 40%
More than, however the specific capacity of positive electrode is but well below the specific capacity of negative electrode material, thus lithium battery has weight under study for action
The application value wanted.
Lithium manganese phosphate is a kind of natural minerals or artificial synthesized ternary electrode material of lithium battery, has olivine shape
Crystal structure, physicochemical properties are stablized when leading to it as electrode material.Battery material dynamic performance is bad mainly should
Caused by the electronic conductance and particle conductance on material bodies phase and surface are low.In lithium manganese phosphate, intra-die lithium ion mobility speed
Degree too low the main reason for being the material electrochemical poor activity.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of graphene compound phosphoric acid manganese lithium material, preparation method benefits
It is with different preparation processes that graphene is compound with lithium manganese phosphate, the electrical property of product is improved, process flow is simple, can batch
Production.
Another object of the present invention is to provide one kind graphene compound phosphoric acid manganese lithium material as made from above-mentioned preparation method
Material, product electrical property are high.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of graphene compound phosphoric acid manganese lithium material preparation method, comprising: lithium hydroxide is dissolved in mixing
In solvent, manganese sulfate solution is sequentially added, graphene oxide solution obtains the first solution；In the condition of ultrasound and stirring, heat preservation
Under, phosphoric acid solution is added into the first solution several times and obtains mixed solution；After carrying out magnetic agitation to mixed solution, it will mix
Solution, which is transferred in reaction kettle, carries out first set reaction, is cooled to room temperature after reaction, continues heating and carries out second of hydro-thermal
Reaction, obtains solid precursor；Solid precursor is mixed with glucose, the heating and calcining in the atmosphere of inert gas.
The present invention proposes a kind of graphene compound phosphoric acid manganese lithium material, is prepared by above-mentioned preparation method.
The beneficial effect of the graphene compound phosphoric acid manganese lithium material of the embodiment of the present invention and preparation method thereof is: by by oxygen
Graphite alkene is uniformly mixed with lithium hydroxide, manganese sulfate, phosphoric acid and carries out secondary water thermal response, so that graphene is in lithium manganese phosphate
It is crystallized on surface uniformly, network structure is constituted, so that the chemical property of lithium manganese phosphate material is improved, using it as lithium-ion electric
The positive electrode in pond solves the problems, such as that lithium manganese phosphate electronic conductivity present in big multiplying power discharging is low and ion diffusion is difficult.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the XRD diagram of the graphene compound phosphoric acid manganese lithium material of the embodiment of the present invention 8；
Fig. 2 is the transmission electron microscope picture of the graphene compound phosphoric acid manganese lithium material of the embodiment of the present invention 8；
Fig. 3 is the high rate performance figure of the graphene compound phosphoric acid manganese lithium material of the embodiment of the present invention 8.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Graphene compound phosphoric acid manganese lithium material of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of graphene compound phosphoric acid manganese lithium material provided in an embodiment of the present invention, comprising:
Lithium hydroxide is dissolved in the mixed solvent, sequentially adds that manganese sulfate solution, that graphene oxide solution obtains first is molten
Liquid；
Specifically, lithium hydroxide LiOHH2O, manganese sulfate MnSO4·4H2The concentration of O, graphene oxide solution is
1g/L.It is more equal in order to mix when being added with the lithia of in the mixed solvent that manganese sulfate and graphene oxide, which are configured to solution,
It is even.Mixed solvent keeps lithium hydroxide, manganese sulfate, graphene oxide mixing more uniform as reaction medium and dispersing agent.
Further, in a preferred embodiment of the present invention, mixed solvent be water, dimethylformamide mixture, water with
The volume ratio of dimethylformamide is 1:2~5.
Under conditions of ultrasound is with stirring, heat preservation, phosphoric acid solution is added into the first solution several times and obtains including white
The mixed solution of precipitating；
Specifically, the weight percent of phosphoric acid solution is 85%.When phosphoric acid solution is added, ultrasound is to make with stirring
Reactant dispersion is more uniform, reaction is more abundant；It is to be added at one time reaction in order to prevent not that phosphoric acid solution is added several times
Sufficiently；By the lot of experiments of inventor, when the temperature of the first solution is maintained at 60~80 DEG C, reaction can be made more to fill
Point, product property is more preferable.
After carrying out magnetic agitation to mixed solution, mixed solution is transferred to progress first time hydro-thermal reaction in reaction kettle,
It is cooled to room temperature after reaction, continues heating and carry out second of hydro-thermal reaction, obtain solid precursor；
Further, in a preferred embodiment of the present invention, to mixed solution carry out magnetic agitation mixing speed be 400~
500r/min, mixing time are 5min~10min.
Further, in a preferred embodiment of the present invention, after mixed solution being transferred to reaction kettle, first time hydro-thermal is carried out
It further include that one of dispersing agent PEG-4000, PEG-6000, Sodium Polyacrylate or several are added into reaction kettle before reaction
Kind.Specifically, reaction kettle is ptfe autoclave.
Further, in a preferred embodiment of the present invention, the reaction temperature of first time hydro-thermal reaction is 180~200 DEG C, instead
It is 8~16h between seasonable.
Further, in a preferred embodiment of the present invention, after first time hydro-thermal reaction, with the rate of 4~5 DEG C/min
It is cooled to room temperature, slow cooling can form good crystalline solid.Continue heating and carry out second of hydro-thermal reaction, second of hydro-thermal is anti-
It filters after answering, washed with ethanol water, and dry second of hydro-thermal reaction product obtains under conditions of 60~80 DEG C
Solid precursor.
Further, in a preferred embodiment of the present invention, the reaction time of second of hydro-thermal reaction is 4~6h, reaction temperature
Degree is 150~180 DEG C.
Further, in a preferred embodiment of the present invention, the molar ratio of lithium hydroxide, manganese sulfate, phosphoric acid, graphene oxide
For 2~6:1:1~3:2~3.
Solid precursor is mixed with glucose, grinding is uniform, the heating and calcining in the atmosphere of inert gas.
Specifically, inert gas is the inert gases such as argon gas or helium, and calcination temperature is 600~700 DEG C.After calcining to obtain the final product
To graphene compound phosphoric acid manganese lithium material.
The electronic conductivity and chemical property and surface texture of lithium manganese phosphate material are closely bound up.Improve lithium manganese phosphate table
Face structure is of great significance to its specific capacity of raising and high rate capability.
Graphene as a kind of new carbon, have as single layer of carbon atom it is tightly packed made of bi-dimensional cellular shape crystal
Structure, unique and perfect structure make it have beneficial property.Graphene conductive is splendid, and electron mobility is high
In carbon nanotube and crystalline silicon, resistivity ratio silver is lower.Since graphene has the graphite-structure of monolayer, so that it has
Very big specific surface area.Surface of graphene oxide is rich in the hydrophilic functional groups such as hydroxyl and carboxyl, can pass through coordinate bond, hydrogen
The absorption such as key, electrostatic interaction are largely cationic, so as to pass through the phase of itself and raw particles using graphene oxide as template
Interaction forms predecessor, and the graphene uniform after making reduction is wrapped in lithium manganese phosphate particle surface.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Graphene compound phosphoric acid manganese lithium material provided in this embodiment is prepared by following preparation method comprising:
By LiOHH2O is dissolved in the in the mixed solvent of water, ethylene glycol, sequentially adds MnSO4·4H2The oxygen of O solution, 1g/L
Graphite alkene solution obtains the first solution；
Into the first solution be added 85wt% phosphoric acid solution obtain include white precipitate mixed solution；
Mixed solution, which is transferred to progress first time hydro-thermal reaction, the reaction temperature of first time hydro-thermal reaction in reaction kettle, is
180 DEG C, reaction time 8h.Cooled to room temperature after reaction is washed through filtering, with ethanol water, is spontaneously dried
Product obtains solid precursor.Lithium hydroxide, manganese sulfate, phosphoric acid, graphene oxide molar ratio be 2:1:3:2.
Solid precursor is mixed with glucose, grinding uniformly, in the atmosphere of argon gas, heating and calcining at 600 DEG C, obtains
Graphene compound phosphoric acid manganese lithium material.
Embodiment 2
Graphene compound phosphoric acid manganese lithium material provided in this embodiment is prepared by following preparation method comprising:
By LiOHH2The in the mixed solvent that O is dissolved in water, dimethylformamide volume ratio is 1:2, sequentially adds MnSO4·
4H2O solution, 1g/L graphene oxide solution obtain the first solution；
Into the first solution be added 85wt% phosphoric acid solution obtain include white precipitate mixed solution；
Mixed solution is transferred in reaction kettle progress first time hydro-thermal reaction, reaction temperature is 200 DEG C, and the reaction time is
16h.It is cooled to room temperature, is washed through filtering, with ethanol water, and in 60 DEG C of item with the rate of 4 DEG C/min after reaction
Desciccate obtains solid precursor under part.Lithium hydroxide, manganese sulfate, phosphoric acid, graphene oxide molar ratio be 6:1:1:3.
Solid precursor is mixed with glucose, grinding uniformly, in the atmosphere of helium, heating and calcining at 700 DEG C, obtains
The compound lithium manganese phosphate material of graphene.
Embodiment 3
Graphene compound phosphoric acid manganese lithium material provided in this embodiment is prepared by following preparation method comprising:
By LiOHH2The in the mixed solvent that O is dissolved in water, dimethylformamide volume ratio is 1:5, sequentially adds MnSO4·
4H2O solution, 1g/L graphene oxide solution obtain the first solution；
Into the first solution be added 85wt% phosphoric acid solution obtain include white precipitate mixed solution；
After being 400r/min to mixed solution low whipping speed, carrying out magnetic agitation under conditions of mixing time is 5min,
Mixed solution is transferred to progress first time hydro-thermal reaction in reaction kettle, the reaction temperature of first time hydro-thermal reaction is 190 DEG C, instead
It is 12h between seasonable.It is cooled to room temperature after reaction with the rate of 5 DEG C/min, is further continued for heating and carries out second of hydro-thermal reaction,
The reaction time of second of hydro-thermal reaction is 4h, and reaction temperature is 150 DEG C.It filters, washed with ethanol water after reaction,
And desciccate obtains solid precursor under conditions of 80 DEG C.Lithium hydroxide, manganese sulfate, phosphoric acid, graphene oxide mole
Than for 4:1:3:3.
Solid precursor is mixed with glucose, grinding uniformly, in the atmosphere of argon gas, heating and calcining at 650 DEG C, obtains
Graphene compound phosphoric acid manganese lithium material.
Embodiment 4
Graphene compound phosphoric acid manganese lithium material provided in this embodiment is prepared by following preparation method comprising:
By LiOHH2The in the mixed solvent that O is dissolved in water, dimethylformamide volume ratio is 1:4, sequentially adds MnSO4·
4H2O solution, 1g/L graphene oxide solution obtain the first solution；
Into the first solution be added 85wt% phosphoric acid solution obtain include white precipitate mixed solution；
After being 500r/min to mixed solution low whipping speed, carrying out magnetic agitation under conditions of mixing time is 10min,
Mixed solution is transferred in reaction kettle, and dispersing agent PEG-4000 and PEG-6000 is added and carries out first time hydro-thermal reaction, the
The reaction temperature of hydro-thermal reaction is 200 DEG C, reaction time 16h.It is cooled to after reaction with the rate of 4.5 DEG C/min
Room temperature is further continued for heating and carries out second of hydro-thermal reaction, and the reaction time of second of hydro-thermal reaction is 6h, reaction temperature 180
℃.It filters, washed with ethanol water after reaction, and desciccate obtains solid precursor under conditions of 70 DEG C.Hydrogen
Lithia, manganese sulfate, phosphoric acid, graphene oxide molar ratio be 2:1:3:3.
Solid precursor is mixed with glucose, grinding uniformly, in the atmosphere of helium, heating and calcining at 600 DEG C, obtains
Graphene compound phosphoric acid manganese lithium material.
Embodiment 5
Graphene compound phosphoric acid manganese lithium material provided in this embodiment is prepared by following preparation method comprising:
By LiOHH2The in the mixed solvent that O is dissolved in water, dimethylformamide volume ratio is 1:3, sequentially adds MnSO4·
4H2O solution, 1g/L graphene oxide solution obtain the first solution；
Under conditions of ultrasound is with stirring, 60 DEG C of heat preservations, the phosphoric acid solution that 85wt% is added into the first solution is wrapped
Include the mixed solution of white precipitate；
After being 450r/min to mixed solution low whipping speed, carrying out magnetic agitation under conditions of mixing time is 8min,
Mixed solution is transferred in reaction kettle, and dispersing agent PEG-6000 is added and carries out first time hydro-thermal reaction, first time hydro-thermal is anti-
The reaction temperature answered is 200 DEG C, reaction time 16h.It is cooled to room temperature, is further continued for the rate of 5 DEG C/min after reaction
Heating carries out second of hydro-thermal reaction, and the reaction time of second of hydro-thermal reaction is 5h, and reaction temperature is 160 DEG C.Reaction terminates
It filters, washed with ethanol water afterwards, and desciccate obtains solid precursor under conditions of 80 DEG C.Lithium hydroxide, sulfuric acid
Manganese, phosphoric acid, graphene oxide molar ratio be 4:1:1:2.
Solid precursor is mixed with glucose, grinding uniformly, in the atmosphere of argon gas, heating and calcining at 700 DEG C, obtains
Graphene compound phosphoric acid manganese lithium material.
Embodiment 6
Graphene compound phosphoric acid manganese lithium material provided in this embodiment is prepared by following preparation method comprising:
By LiOHH2The in the mixed solvent that O is dissolved in water, dimethylformamide volume ratio is 1:2, sequentially adds MnSO4·
4H2O solution, 1g/L graphene oxide solution obtain the first solution；
Under conditions of ultrasound is with stirring, 80 DEG C of heat preservations, point 2 phosphoric acid solutions that 85wt% is added into the first solution are obtained
To the mixed solution including white precipitate；
After being 400r/min to mixed solution low whipping speed, carrying out magnetic agitation under conditions of mixing time is 5min,
Mixed solution is transferred in reaction kettle, and dispersing agent Sodium Polyacrylate is added and carries out first time hydro-thermal reaction, first time hydro-thermal
The reaction temperature of reaction is 180 DEG C, reaction time 8h.It is cooled to room temperature, is further continued for the rate of 4 DEG C/min after reaction
Heating carries out second of hydro-thermal reaction, and the reaction time of second of hydro-thermal reaction is 4h, and reaction temperature is 150 DEG C.Reaction terminates
It filters, washed with ethanol water afterwards, and desciccate obtains solid precursor under conditions of 60 DEG C.Lithium hydroxide, sulfuric acid
Manganese, phosphoric acid, graphene oxide molar ratio be 2:1:1:2.
Solid precursor is mixed with glucose, grinding uniformly, in the atmosphere of argon gas, heating and calcining at 600 DEG C, obtains
Graphene compound phosphoric acid manganese lithium material.
Embodiment 7
Graphene compound phosphoric acid manganese lithium material provided in this embodiment is prepared by following preparation method comprising:
By LiOHH2The in the mixed solvent that O is dissolved in water, dimethylformamide volume ratio is 1:5, sequentially adds MnSO4·
4H2O solution, 1g/L graphene oxide solution obtain the first solution；
Under conditions of ultrasound is with stirring, 70 DEG C of heat preservations, point 5 phosphoric acid solutions that 85wt% is added into the first solution are obtained
To the mixed solution including white precipitate；
After being 500r/min to mixed solution low whipping speed, carrying out magnetic agitation under conditions of mixing time is 10min,
Mixed solution is transferred in reaction kettle, and dispersing agent PEG-4000 is added and carries out first time hydro-thermal reaction, first time hydro-thermal is anti-
The reaction temperature answered is 200 DEG C, reaction time 16h.It is cooled to room temperature, is further continued for the rate of 5 DEG C/min after reaction
Heating carries out second of hydro-thermal reaction, and the reaction time of second of hydro-thermal reaction is 6h, and reaction temperature is 180 DEG C.Reaction terminates
It filters, washed with ethanol water afterwards, and desciccate obtains solid precursor under conditions of 70 DEG C.Lithium hydroxide, sulfuric acid
Manganese, phosphoric acid, graphene oxide molar ratio be 6:1:3:3.
Solid precursor is mixed with glucose, grinding uniformly, in the atmosphere of argon gas, heating and calcining at 700 DEG C, obtains
Graphene compound phosphoric acid manganese lithium material.
Embodiment 8
Graphene compound phosphoric acid manganese lithium material provided in this embodiment is prepared by following preparation method comprising:
By LiOHH2The in the mixed solvent that O is dissolved in water, dimethylformamide volume ratio is 1:3, sequentially adds MnSO4·
4H2O solution, 1g/L graphene oxide solution obtain the first solution；
Under conditions of ultrasound is with stirring, 80 DEG C of heat preservations, point 5 phosphoric acid solutions that 85wt% is added into the first solution are obtained
To the mixed solution including white precipitate；
After being 500r/min to mixed solution low whipping speed, carrying out magnetic agitation under conditions of mixing time is 10min,
Mixed solution is transferred in reaction kettle, and dispersing agent PEG-4000 is added and carries out first time hydro-thermal reaction, first time hydro-thermal is anti-
The reaction temperature answered is 200 DEG C, reaction time 12h.It is cooled to room temperature, is further continued for the rate of 5 DEG C/min after reaction
Heating carries out second of hydro-thermal reaction, and the reaction time of second of hydro-thermal reaction is 5h, and reaction temperature is 160 DEG C.Reaction terminates
It filters, washed with ethanol water afterwards, and desciccate obtains solid precursor under conditions of 80 DEG C.Lithium hydroxide, sulfuric acid
Manganese, phosphoric acid, graphene oxide molar ratio be 3:1:1:3.
Solid precursor is mixed with glucose, grinding uniformly, in the atmosphere of argon gas, heating and calcining at 600 DEG C, obtains
Graphene compound phosphoric acid manganese lithium material.
The exterior appearance of the graphene compound phosphoric acid manganese lithium material of embodiment 1-8 is observed, as a result such as table 1.
1 exterior appearance contrast table of table
As shown in Table 1, graphene compound phosphoric acid manganese lithium material exterior appearance made from Examples 1 to 8 has larger difference,
The shape of middle embodiment 8 is more excellent, soilless sticking, and particle is uniform.Below for embodiment 8 graphene compound phosphoric acid manganese lithium material into
Row characterization test.
Using X ' the pert TRO MPD type polycrystalline of Philips Corporate turn target x-ray diffractometer (Cu target K alpha ray λ=
0.15406nm), Ni filter plate, tube current 20mA, tube voltage 20kV, 2 θ=10~80 ° of scanning angle, 8 ° of scanning speed/
min.X-ray diffraction is carried out to the hollow sphere positive electrode of embodiment 8, it is as shown in Figure 1 to obtain XRD spectrum.
Transmission electron microscope analysis, the knot of obtained transmission electron microscope are carried out to the graphene compound phosphoric acid manganese lithium material of embodiment 8
Fruit is as shown in Figure 2.
Characterization can be carried out using electrochemistry of the CR2032 type button cell to synthetic material.Using Shenzhen Neware company
BTS test macro 2.0~4.8V carries out constant current charge-discharge test, wherein 1C=200mAh/g at room temperature.Fig. 3 is embodiment
The high rate performance figure of 8 graphene compound phosphoric acid manganese lithium material.
The XRD spectra of the graphene compound phosphoric acid manganese lithium material of embodiment 8 and standard spectrogram kissing as can be seen from Figure 1
It closes, and the sharp free from admixture peak of peak type occurs, illustrates that the preparation method of embodiment 8 can be prepared and carry out complete lithium manganese phosphate material
Material.
The graphene compound phosphoric acid manganese lithium material even particle distribution of embodiment 8 as can be seen from Figure 2, soilless sticking phenomenon.
The graphene compound phosphoric acid manganese lithium material of embodiment 8 first discharge specific capacity in 0.1C is as can be seen from Figure 3
152.1mAh/g, specific discharge capacity is 103.4mAh/g after recycling 30 times, and there is no significantly decaying for the specific volume of material.
In conclusion the preferred embodiment of graphene compound phosphoric acid manganese lithium material of the embodiment of the present invention and preparation method thereof
In, by the way that graphene oxide to be uniformly mixed to lithium hydroxide, manganese sulfate, phosphoric acid and carried out secondary water thermal response, so that graphite
Alkene crystallizes uniformly on lithium manganese phosphate surface, network structure is constituted, so that the chemical property of lithium manganese phosphate material is improved, with it
As the positive electrode of lithium ion battery, solve lithium manganese phosphate big multiplying power put a little present in electronic conductivity is low and ion expansion
Dissipate difficult problem.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (6)
1. a kind of preparation method of graphene compound phosphoric acid manganese lithium material characterized by comprising
Lithium hydroxide is dissolved in the mixed solvent, sequentially adds manganese sulfate solution, graphene oxide solution obtains the first solution；?
Phosphoric acid solution is added into first solution several times and obtains mixed solution under conditions of stirring, heat preservation for ultrasound, and described the
The temperature of one solution is 60 ~ 80 DEG C；
After carrying out magnetic agitation to the mixed solution, it is anti-that the mixed solution is transferred to progress first time hydro-thermal in reaction kettle
Answer, the reaction temperature of the first time hydro-thermal reaction is 180 ~ 200 DEG C, and the reaction time is 8 ~ 12h, after reaction with 4 ~ 5 DEG C/
The rate of min is cooled to room temperature, and is continued heating and is carried out second of hydro-thermal reaction, the reaction time of second of hydro-thermal reaction is
4 ~ 6h, reaction temperature are 150 ~ 180 DEG C, through being filtered, washed after second of hydro-thermal reaction, and in 60 ~ 80 DEG C of item
Dry second of hydro-thermal reaction product obtains solid precursor under part；
The solid precursor is mixed with glucose, the heating and calcining in the atmosphere of inert gas.
2. the preparation method of graphene compound phosphoric acid manganese lithium material according to claim 1, which is characterized in that will be described mixed
It further include being added into the reaction kettle before carrying out the first time hydro-thermal reaction after conjunction solution is transferred to the reaction kettle
One or more of dispersing agent PEG-4000, PEG-6000, Sodium Polyacrylate.
3. the preparation method of graphene compound phosphoric acid manganese lithium material according to claim 1, which is characterized in that described mixed
Closing solution and carrying out the mixing speed of magnetic agitation is 400 ~ 500r/min, and mixing time is 5min ~ 10min.
4. the preparation method of graphene compound phosphoric acid manganese lithium material according to claim 1, which is characterized in that the mixing
Solvent is the mixture of water, dimethylformamide, and the volume ratio of the water and the dimethylformamide is 1:2 ~ 5.
5. the preparation method of graphene compound phosphoric acid manganese lithium material according to claim 1, which is characterized in that described mixed
Close solution in, the lithium hydroxide, manganese sulfate, phosphoric acid, graphene oxide molar ratio be 2 ~ 6:1:1 ~ 3:2 ~ 3.
6. a kind of graphene compound phosphoric acid manganese lithium material, which is characterized in that by graphene described in any one of claim 1 to 5
The preparation method of compound phosphoric acid manganese lithium material is prepared.
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| CN105655561A (en) * | 2016-02-29 | 2016-06-08 | 苏州迪思伏新能源科技有限公司 | Synthesis method of lithium manganese phosphate nanosheets |
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