CN109616633A - A kind of preparation method of nano-sheet manganese phosphate anode material for lithium-ion batteries - Google Patents
A kind of preparation method of nano-sheet manganese phosphate anode material for lithium-ion batteries Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
This application involves a kind of preparation methods of preparation method positive electrode in expanded graphite surface in situ growth nano-sheet manganese-lithium phosphate anode material, by expanded graphite during the reaction to the inhibiting effect of the crystal growth of material and reunion, so that lithium manganese phosphate particle has good dispersibility, simultaneously under the collective effect of the solvent containing hydroxyl and expanded graphite, manganese phosphate lithium nanosheet is grown along (020) the advantage crystal face for being conducive to lithium ion insertion abjection, and manganese phosphate lithium nanosheet is mutually compound in the form of surface-to-surface contact with expanded graphite, form good conductive network, greatly improve the high rate performance and cyclical stability of material.The material can satisfy the requirement of power lithium-ion battery fast charging and discharging under high current, have a good application prospect in power battery field.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries and electrochemical field, and in particular to a kind of in expanded graphite surface original
The preparation method of the preparation method positive electrode of position growth nano-sheet manganese-lithium phosphate anode material.
Background technique
As the demand to electric car and hybrid vehicle is constantly aggravated, the development of anode material for lithium-ion batteries is not
It is disconnected to accelerate.Important representative of the LiFePO4 as anode material for lithium-ion batteries, business application are very mature.And and ferric phosphate
The identical lithium manganese phosphate of crystalline lithium structure has 170mAhg-1High theoretical capacity, cyclical stability is also close with LiFePO4, and
The high voltage platform for the 4.1V that lithium manganese phosphate possesses makes the energy density of full battery improve 20% or so than LiFePO4, this
One characteristic causes the highest attention of people, this material be considered as commercialized positive electrode most prospect replace
Dai Pin, however due to self structure caused by poorly conductive, the disadvantages such as ion diffusion rates are low, cause its there are it is long when
Between recycle after inducing capacity fading it is serious and the problems such as high rate performance is poor, these problems greatly limit their application and develop.
The method for improving lithium manganese phosphate chemical property at present mainly has: one, synthesis has the lithium manganese phosphate of special crystal face
Nanoparticle, by lithium manganese phosphate molecular structure carry out the study found that the lithium ion in lithium manganese phosphate molecule be along
(010) direction carries out one-dimensional diffusion, therefore shortens ion diffusion length to improve ion diffusion rates as improvement manganese phosphate
The main method of lithium electrochemical performance has the manganese phosphate nano particle of (010) special crystal face by synthesizing, can effectively improve
Ion diffusion rates.A.2014 such as [J] Hui Guo et alJournal of Materials Chemistry, 2,10581-
10588.Two, one layer of conductive coating is coated to improve lithium manganese phosphate electric conductivity on surface.Recent years graphene and reduction-oxidation
Graphene has application as carbon material in many electrode active materials, but its easy to reunite and surface oxygen functional group reduction is not
The shortcomings that its electric conductivity can thoroughly be reduced.Graphene or redox graphene are as load surface and electrochemical active material simultaneously
The different way of contact of particle also influences the electric conductivity of material, such as point-face contact, the inefficient electronic contact mode such as line-face contact,
It is extremely limited to the improvement of chemical property, graphene or reduction-oxidation graphite can be made full use of by the way of surface-to-surface contact
Alkene electric conductivity.Expanded graphite has and high-specific surface area similar in graphite and distinctive layering as one kind of graphite material
Structure makes it not easy to reunite, and relative to graphene oxide, the amount of expanded graphite oxygen-containing functional group greatly reduces, therefore adopts
Use expanded graphite that can greatly improve the electric conductivity of material as conductive network.
The characteristics of present invention attempts to use expanded graphite surface with part oxygen-containing functional group, in combination with there is hydroxyl
Organic solvent carry out solvent thermal reaction so that with (020) advantage crystal face manganese phosphate lithium nanosheet on expanded graphite surface
Growth in situ, good dispersion between particle and particle, and be in contact in such a way that surface-to-surface is in contact with expanded graphite, it is made
Standby material is having excellent stable circulation performance and high rate performance, especially high rate capability, meet electric car and
Requirement of the hybrid vehicle to anode material for lithium-ion batteries.
Summary of the invention
The technical problem to be solved by the present invention is to solve deficiency in the prior art, to provide a kind of nano-sheet
The preparation method of manganese phosphate anode material for lithium-ion batteries.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of nano-sheet manganese phosphate anode material for lithium-ion batteries, comprising:
Expanded graphite is added containing in alcohol type organic, lithium salts is dissolved in wherein, is configured to solution A, wherein solution A
Middle lithium concentration be 0.1-3.5mol/L, elemental lithium, expanded graphite mass ratio be 0.45-2.3: 1；
Phosphorus source is dissolved in containing the solution B that phosphate concentration is 0.03-2.6mol/L is configured in alcohol type organic, it will
Solution B is added in solution A is configured to solution C under agitation, wherein the solvent volume of the solvent of solution B and solution A ratio
It is 0.4-0.8: 1；
Manganese source is dissolved in the solution that manganese ion concentration 0.025-2.2mol/L is made into alcohol type organic and water mixed solvent
D；
Solution D is mixed with solution C under stirring conditions, wherein the solvent volume of the solvent of solution D and solution A ratio is
0.5-1.0: 1, and controlling reaction temperature is 140-220 DEG C, reaction time 6-20h after the reaction was completed filters products therefrom
And washed repeatedly with alcohols and deionized water, until filtrate pH value is 6-7, precursor powder is obtained after dry；
After precursor powder is mixed with carbon source, be warming up to 400-900 DEG C under a shielding gas, after keeping the temperature the 2-8h time with
Furnace is cooled to room temperature to arrive the nano-sheet manganese-lithium phosphate anode material grown in expanded graphite surface in situ.
Preferably, preparation method of the invention, the expanded graphite are by graphite oxide under a shielding gas in 400-
900 DEG C of calcining 1-4h are obtained；
The expanded graphite, which is added in solvent, passes through ultrasonication 1h or more.
Preferably, preparation method of the invention,
Described is the mixing of ethyl alcohol or ethylene glycol or ethyl alcohol, ethylene glycol and deionized water containing alcohol type organic solvent
Object.
Preferably, preparation method of the invention, the manganese source are at least one of manganese sulfate, manganese acetate, manganese nitrate.
Preferably, preparation method of the invention, phosphorus source are at least one of phosphoric acid, ammonium dihydrogen phosphate.
Preferably, preparation method of the invention, the carbon source be sucrose, glucose, dopamine, polypyrrole, phenolic resin,
At least one of cetyl trimethylammonium bromide, polyvinylpyrrolidone.
Preferably, preparation method of the invention, the lithium salts are at least one of lithium acetate, lithium hydroxide, lithium carbonate.
Preferably, preparation method of the invention, after precursor powder is mixed with carbon source, the heating rate of heating is 2-6 DEG C/
min。
Preferably, preparation method of the invention, it is characterised in that: the protective gas is nitrogen, argon gas or nitrogen and hydrogen
The mixed gas or argon gas of gas and the mixed gas of hydrogen；In the mixed gas of the nitrogen and hydrogen, nitrogen accounts for 80~
99V%, hydrogen account for 1~20V%；In the mixed gas of the argon gas and hydrogen, argon gas accounts for 80~99V%, and hydrogen accounts for 1~
20V%.
A kind of nano-sheet manganese phosphate anode material for lithium-ion batteries of the invention, is prepared by above-mentioned preparation method
It arrives.
The beneficial effects of the present invention are:
(1) present invention is using a kind of nano-sheet lithium manganese phosphate in the growth of expanded graphite surface in situ of solvent structure
Positive electrode has many advantages, such as that synthesis technology is simple, reproducible.
(2) present invention has synthesized a kind of nano-sheet manganese-lithium phosphate anode material in the growth of expanded graphite surface in situ,
Wherein expanded graphite is during the reaction to the inhibiting effect of the crystal growth of material and reunion, so that lithium manganese phosphate particle has
Have good dispersibility, while under the collective effect of the solvent containing hydroxyl and expanded graphite, manganese phosphate lithium nanosheet along
Be conducive to (020) advantage crystal face growth of lithium ion insertion abjection, and manganese phosphate lithium nanosheet and expanded graphite are connect with surface-to-surface
The form of touching is mutually compound, forms good conductive network, greatly improves the high rate performance and cyclical stability of material.It should
Material can satisfy the requirement of power lithium-ion battery fast charging and discharging under high current, have in power battery field good
Application prospect.
Detailed description of the invention
The technical solution of the application is further illustrated with reference to the accompanying drawings and examples.
Fig. 1 is in embodiment 1 in the X-ray of the nano-sheet manganese-lithium phosphate anode material of expanded graphite surface in situ growth
Diffraction (XRD) figure.
Fig. 2 is in embodiment 1 in the scanning of the nano-sheet manganese-lithium phosphate anode material of expanded graphite surface in situ growth
Electronic Speculum (SEM) figure and transmission electron microscope (TEM) figure.
Fig. 3 be embodiment 1 in expanded graphite surface in situ growth nano-sheet manganese-lithium phosphate anode material for the first time
Charging and discharging curve.
Fig. 4 is in embodiment 1 in the circulation of the nano-sheet manganese-lithium phosphate anode material of expanded graphite surface in situ growth
Performance map.
Fig. 5 is in embodiment 1 in the multiplying power of the nano-sheet manganese-lithium phosphate anode material of expanded graphite surface in situ growth
Performance map.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.
It is described in detail the technical solution of the application below with reference to the accompanying drawings and in conjunction with the embodiments.
Embodiment 1
A kind of preparation side of the nano-sheet manganese-lithium phosphate anode material in the growth of expanded graphite surface in situ of the present embodiment
Method, comprising the following steps:
(1) graphite oxide is obtained into expanded graphite in 400 DEG C of calcining 2h under protection of argon gas first；
(2) it by step (1) products therefrom, is added into the solvent of 20mL ethylene glycol, ultrasonic disperse 1h, it will after ultrasound
Lithium hydroxide is dissolved in the uniform solution A for being wherein configured to that lithium concentration is 0.1mol/L, wherein elemental lithium, expanded graphite
Mass ratio is 2.5: 1；
(3) phosphoric acid is dissolved in the solution B for being configured to that phosphate concentration is 0.03mol/L in 15mL ethylene glycol, in stirring bar
Solution B is added in solution A under part, as solution C.
(4) manganese sulfate is dissolved in 18mL (ratio of ethylene glycol and water is 5: 1) and is made into manganese ion concentration 0.025mol/L's
Solution D.Solution D is mixed with solution C under stirring conditions.
(5) step (4) resulting mixed solution is transferred to the stainless steel cauldron with polytetrafluoroethylene material liner
In, sealing is placed in drying box；Controlling reaction temperature is 140 DEG C, reaction time 6h, after the reaction was completed, by products therefrom
It filters and is washed repeatedly with ethyl alcohol and deionized water, until filtrate pH value is 6, obtain precursor after forced air drying at 60 DEG C
End.
(6) step (5) obtained precursor powder is mixed to be placed on sucrose and is reacted in kiln, under protection of argon gas
500 DEG C are warming up to 2 DEG C/min, room temperature is cooled to after keeping the temperature the 2h time with the furnace and is grown to get in expanded graphite surface in situ
Nano-sheet manganese-lithium phosphate anode material.
Fig. 1 is 1 gained LiMnPO of the embodiment of the present invention4The XRD diagram of@EG@C positive electrode material.It will be seen from figure 1 that the material
The diffraction maximum of material is sharp, and crystallinity is higher, and grain development is perfect.Fig. 2 a is 1 gained LiMnPO of the embodiment of the present invention4@EG@C is just
The SEM of pole material, Fig. 2 b are 1 gained LiMnPO of the embodiment of the present invention4The TEM of@EG C positive electrode material schemes, can be with from two width figures
Find out, the manganese phosphate lithium nanosheet that average grain diameter is about 20~150nm is grown in expanded graphite surface and interlayer.
With N-Methyl pyrrolidone (NMP) for solvent, by the LiMnPO4@EG@C-material synthesized in the present embodiment and gather inclined
Vinyl fluoride (PVDF) and acetylene black are to be uniformly mixed and coated in aluminium foil at 80: 10: 10 in mass ratio, and anode pole piece is made, then
Using lithium piece as cathode, be assembled into lithium ion battery, measure at room temperature, under the conditions of 0.2C (1C=170mA/g), 2.0-4.5V its
First discharge specific capacity is up to 142mAh/g, sees Fig. 3；Under the conditions of 1C, 2.0-4.5V by 200 times circulation after capacity retention ratio
It is 100%, sees Fig. 4；Putting a specific capacity for the first time under the conditions of 10C, 2.0-4.6V is that 103mAh/g is put after 1000 circulations
Electric specific capacity is 72mAh/g, and electro-chemical test shows the LiMnPO synthesized in the present embodiment4@EG@C-material is compared to comparison
Example, capacity retention ratio is improved significantly, while still having under high current density and relatively high to put a specific capacity and circulation
Stability has excellent chemical property.
Embodiment 2
A kind of preparation side of the nano-sheet manganese-lithium phosphate anode material in the growth of expanded graphite surface in situ of the present embodiment
Method, comprising the following steps:
(1) graphite oxide is obtained into expanded graphite in 700 DEG C of calcining 4h under nitrogen protection first；
(2) it by step (1) products therefrom, is added into the solvent of 40mL alcohol, ultrasonic disperse 2h, by second after ultrasound
Sour lithium is dissolved in the uniform solution A for being wherein configured to that lithium concentration is 0.3mol/L, wherein the quality of elemental lithium, expanded graphite
Than being 5: 1；
(3) ammonium di-hydrogen phosphate is dissolved in the solution B for being configured to that phosphate concentration is 0.09mol/L in 16mL ethylene glycol,
Solution B is added in solution A under stirring condition, as solution C.
(4) manganese acetate is dissolved in 20mL (ratio of ethylene glycol and water is 4: 1) and is made into the molten of manganese ion concentration 0.12mol/L
Liquid D.Solution D is mixed with solution C under stirring conditions.
(5) step (4) resulting mixed solution is transferred to the stainless steel cauldron with polytetrafluoroethylene material liner
In, sealing is placed in drying box；Controlling reaction temperature is 160 DEG C, reaction time 8h, after the reaction was completed, by products therefrom
It filters and is washed repeatedly with ethyl alcohol and deionized water, until filtrate pH value is 7, obtain precursor after forced air drying at 80 DEG C
End.
(6) step (5) obtained precursor powder is mixed to be placed on cetyl trimethylammonium bromide and reacts kiln
In furnace, 600 DEG C are warming up to 4 DEG C/min under nitrogen protection, cool to room temperature after keeping the temperature the 2h time with the furnace to get to expanding
The nano-sheet manganese-lithium phosphate anode material of graphite surface growth in situ.
Method same as Example 1 is made lithium ion battery, electro-chemical test show 0.2C, 0.5C, 1C, 2C, 5C,
Under 10C, 20C, 30C multiplying power, specific discharge capacity be respectively 145.4mAh/g, 131mAh/g, 123mAh/g, 118mAh/g,
115mAh/g, 102mAh/g, 82mAh/g and 70mAh/g are shown in Fig. 5.
Embodiment 3
A kind of preparation side of the nano-sheet manganese-lithium phosphate anode material in the growth of expanded graphite surface in situ of the present embodiment
Method, comprising the following steps:
(1) by graphite oxide, in atmosphere protection, (for the mixed gas of nitrogen and hydrogen, (nitrogen accounts for 80V%, and hydrogen accounts for first
Expanded graphite is obtained in 800 DEG C of calcining 2h under 20V%)；
(2) by step (1) products therefrom, the in the mixed solvent into 30mL deionized water and ethylene glycol, ultrasonic disperse is added
Lithium carbonate is dissolved in the uniform solution A for being wherein configured to that lithium concentration is 0.2mol/L, wherein lithium member by 1h after ultrasonic
Plain, expanded graphite mass ratio is 7: 1；
(3) phosphoric acid is dissolved in and is configured to the solution that phosphate concentration is 0.12mol/L in 15mL deionized water and ethylene glycol
Solution B is added in solution A by B under agitation, as solution C.
(4) manganese nitrate is dissolved in 18mL (ratio of ethylene glycol and water is 5: 1) and is made into the molten of manganese ion concentration 0.14mol/L
Liquid D.Solution D is mixed with solution C under stirring conditions.
(5) step (4) resulting mixed solution is transferred to the stainless steel cauldron with polytetrafluoroethylene material liner
In, sealing is placed in drying box；Controlling reaction temperature is 180 DEG C, reaction time 10h, after the reaction was completed, by products therefrom
It filters and is washed repeatedly with ethyl alcohol and deionized water, until filtrate pH value is 7, obtain precursor after forced air drying at 90 DEG C
End.
(6) step (5) obtained precursor powder is mixed to be placed on dopamine and is reacted in kiln, in nitrogen and hydrogen
600 DEG C are warming up to 4 DEG C/min under mixed gas (nitrogen accounts for 80V%, and hydrogen the accounts for 20V%) protection of gas, after keeping the temperature the 4h time
Room temperature is cooled to the furnace to get the nano-sheet manganese-lithium phosphate anode material grown in expanded graphite surface in situ is arrived.
Lithium ion battery is made in method same as Example 1, and electro-chemical test shows in 0.2C, 2.0-4.5V voltage
First discharge specific capacity is 137mAh/g in range；Capacity retention ratio is after/200 circulations under the conditions of 1C, 2.0-4.5V
98%, it is shown that good chemical property.
Embodiment 4
A kind of nano-sheet manganese-lithium phosphate anode material in the growth of expanded graphite surface in situ of the present embodiment, including it is following
Step:
(1) graphite oxide is obtained into expanded graphite in 800 DEG C of calcining 4h under atmosphere protection first；
(2) it by step (1) products therefrom, is added into the solvent of 35mL ethyl alcohol, ultrasonic disperse 1.5h, it will after ultrasound
Lithium hydroxide is dissolved in the uniform solution A for being wherein configured to that lithium concentration is 0.3mol/L, wherein elemental lithium, expanded graphite
Mass ratio is 5: 1；
(3) ammonium di-hydrogen phosphate is dissolved in and is configured to phosphate concentration in 15mL (ratio of second alcohol and water be 4: 1) and is
Solution B, is added in solution A by the solution B of 0.09mol/L under agitation, as solution C.
(4) manganese sulfate is dissolved in the solution that manganese ion concentration 1.1mol/L is made into 18mL (ratio of second alcohol and water is 5: 1)
D.Solution D is mixed with solution C under stirring conditions.
(5) step (4) resulting mixed solution is transferred to the stainless steel cauldron with polytetrafluoroethylene material liner
In, sealing is placed in drying box；Controlling reaction temperature is 200 DEG C, reaction time 15h, after the reaction was completed, by products therefrom
It filters and is washed repeatedly with ethyl alcohol and deionized water, until filtrate pH value is 7, obtain precursor after forced air drying at 90 DEG C
End.
(6) step (5) obtained precursor powder is mixed to be placed on polypyrrole and is reacted in kiln, in nitrogen and hydrogen
Be warming up to 650 DEG C under mixed gas (nitrogen accounts for 99V%, and hydrogen the accounts for 1V%) protection of gas with 5 DEG C/min, after keeping the temperature the 6h time with
Furnace is cooled to room temperature to arrive the nano-sheet manganese-lithium phosphate anode material grown in expanded graphite surface in situ.
Lithium ion battery is made in method same as Example 1, and electro-chemical test shows in 0.2C, 2.0-4.5V voltage
First discharge specific capacity is 139mAh/g in range；Capacity retention ratio is after/200 circulations under the conditions of 1C, 2.0-4.5V
95%, it is shown that good chemical property.
Embodiment 5
A kind of nano-sheet manganese-lithium phosphate anode material in the growth of expanded graphite surface in situ of the present embodiment, including it is following
Step:
(1) by graphite oxide, in atmosphere protection, (for the mixed gas of argon gas and hydrogen, (argon gas accounts for 80V%, and hydrogen accounts for first
Expanded graphite is obtained in 800 DEG C of calcining 2h under 20V%))；
(2) it by step (1) products therefrom, is added into the solvent of 40mL ethylene glycol, ultrasonic disperse 1h, it will after ultrasound
Lithium hydroxide is dissolved in the uniform solution A for being wherein configured to that lithium concentration is 0.4mol/L, wherein elemental lithium, expanded graphite
Mass ratio is 5: 1；
(3) phosphoric acid is dissolved in to be configured to phosphate concentration in 30mL (ratio of ethylene glycol and water is 4: 1) be 0.09mol/L's
Solution B is added in solution A by solution B under agitation, as solution C.
(4) manganese sulfate is dissolved in the solution D that manganese ion concentration 2.0/L is made into 20mL ethylene glycol.By solution D in stirring
Under the conditions of mixed with solution C.
(5) step (4) resulting mixed solution is transferred to the stainless steel cauldron with polytetrafluoroethylene material liner
In, sealing is placed in drying box；Controlling reaction temperature is 220 DEG C, reaction time 20h, after the reaction was completed, by products therefrom
It filters and is washed repeatedly with ethyl alcohol and deionized water, until filtrate pH value is 6.5, obtain forerunner after forced air drying at 100 DEG C
Body powder.
(6) step (5) obtained precursor powder is mixed to be placed on polyvinylpyrrolidone and is reacted in kiln,
400 DEG C are warming up to 5 DEG C/min under the protection of the mixed gas (argon gas accounts for 80V%, and hydrogen accounts for 20V%) of argon gas and hydrogen, heat preservation
Room temperature is cooled to after the 8h time with the furnace to get the nano-sheet lithium manganese phosphate anode material grown in expanded graphite surface in situ is arrived
Material.
Lithium ion battery is made in method same as Example 1, and electro-chemical test shows in 0.2C, 2.0-4.5V voltage
First discharge specific capacity is 141mAh/g in range；Capacity retention ratio is after/200 circulations under the conditions of 1C, 2.0-4.5V
100%, it is shown that good chemical property.
Embodiment 6
A kind of nano-sheet manganese-lithium phosphate anode material in the growth of expanded graphite surface in situ of the present embodiment, including it is following
Step:
(1) graphite oxide is obtained into expanded graphite in 900 DEG C of calcining 2h under atmosphere protection first；
(2) it by step (1) products therefrom, is added into the solvent of 30mL ethyl alcohol, ultrasonic disperse 1h, by hydrogen after ultrasound
Lithia is dissolved in the uniform solution A for being wherein configured to that lithium concentration is 0.4mol/L, wherein the matter of elemental lithium, expanded graphite
Amount is than being 5: 1；
(3) phosphoric acid is dissolved in to be configured to phosphate concentration in 20mL (ratio of second alcohol and water is 4: 1) be the molten of 2.0mol/L
Solution B, is added in solution A by liquid B under agitation, as solution C.
(4) manganese sulfate is dissolved in the solution D that manganese ion concentration 2.2/L is made into 20mL ethyl alcohol.By solution D stirring item
It is mixed under part with solution C.
(5) step (4) resulting mixed solution is transferred to the stainless steel cauldron with polytetrafluoroethylene material liner
In, sealing is placed in drying box；Controlling reaction temperature is 220 DEG C, reaction time 20h, after the reaction was completed, by products therefrom
It filters and is washed repeatedly with ethyl alcohol and deionized water, until filtrate pH value is 6.5, obtain forerunner after forced air drying at 100 DEG C
Body powder.
(6) step (5) obtained precursor powder is mixed to be placed on glucose and is reacted in kiln, in argon gas and hydrogen
Be warming up to 700 DEG C under mixed gas (argon gas accounts for 95V%, and hydrogen the accounts for 5V%) protection of gas with 5 DEG C/min, after keeping the temperature the 8h time with
Furnace is cooled to room temperature to arrive the nano-sheet manganese-lithium phosphate anode material grown in expanded graphite surface in situ.
Lithium ion battery is made in method same as Example 1, and electro-chemical test shows in 0.2C, 2.0-4.5V voltage
First discharge specific capacity is 136mAh/g in range；Capacity retention ratio is after/200 circulations under the conditions of 1C, 2.0-4.5V
94%, it is shown that good chemical property.
Embodiment 7
A kind of nano-sheet manganese-lithium phosphate anode material in the growth of expanded graphite surface in situ of the present embodiment, including it is following
Step:
(1) graphite oxide is obtained into expanded graphite in 900 DEG C of calcining 2h under atmosphere protection first；
(2) it by step (1) products therefrom, is added into the solvent of 30mL ethyl alcohol, ultrasonic disperse 1h, by hydrogen after ultrasound
Lithia is dissolved in the uniform solution A for being wherein configured to that lithium concentration is 3.5mol/L, wherein the matter of elemental lithium, expanded graphite
Amount is than being 5: 1；
(3) phosphoric acid is dissolved in to be configured to phosphate concentration in 24mL (ratio of second alcohol and water is 4: 1) be the molten of 2.6mol/L
Solution B, is added in solution A by liquid B under agitation, as solution C.
(4) manganese sulfate is dissolved in the solution D that manganese ion concentration 0.1mol/L is made into 30mL ethyl alcohol.Solution D is being stirred
Under conditions of mixed with solution C.
(5) step (4) resulting mixed solution is transferred to the stainless steel cauldron with polytetrafluoroethylene material liner
In, sealing is placed in drying box；Controlling reaction temperature is 220 DEG C, reaction time 20h, after the reaction was completed, by products therefrom
It filters and is washed repeatedly with ethyl alcohol and deionized water, until filtrate pH value is 6.5, obtain forerunner after forced air drying at 100 DEG C
Body powder.
(6) step (5) obtained precursor powder and phenolic resin are mixed to be placed on and reacts in kiln, in argon gas and
The mixed gas (argon gas accounts for 99V%, and hydrogen accounts for 1V%) of hydrogen is warming up to 900 DEG C under protection with 6 DEG C/min, keeps the temperature the 8h time
Cool to room temperature with the furnace afterwards to get the nano-sheet manganese-lithium phosphate anode material grown in expanded graphite surface in situ is arrived.
Lithium ion battery is made in method same as Example 1, and electro-chemical test shows in 0.2C, 2.0-4.5V voltage
First discharge specific capacity is 128mAh/g in range；Capacity retention ratio is after/200 circulations under the conditions of 1C, 2.0-4.5V
93%, it is shown that good chemical property.
Comparative example
(1) lithium hydroxide is dissolved in 30mL ethylene glycol, is configured to the uniform solution A that lithium concentration is 0.6mol/L.
(3) phosphoric acid is dissolved in to be configured to phosphate concentration in 30mL (ratio of ethylene glycol and water is 4: 1) be 0.4mol/L's
Solution B is added in solution A by solution B under agitation, as solution C.
(4) manganese sulfate is dissolved in the solution D that the dense 0.4mol/L of manganese ion is made into 30mL ethylene glycol.Solution D is being stirred
Under conditions of mixed with solution C.
(5) step (4) resulting mixed solution is transferred to the stainless steel cauldron with polytetrafluoroethylene material liner
In, sealing is placed in drying box；Controlling reaction temperature is 200 DEG C, reaction time 10h, after the reaction was completed, by products therefrom
It filters and is washed repeatedly with ethyl alcohol and deionized water, until filtrate pH value is 6.5, obtain forerunner after forced air drying at 100 DEG C
Body powder.
(6) step (5) obtained precursor powder is mixed to be placed on glucose and is reacted in kiln, in Ar/H2(Ar
Account for 95V%, H2Account for 5V%) 600 DEG C are warming up to 5 DEG C/min under protection, room temperature is cooled to the furnace after keeping the temperature the 2h time to get arriving
In the nano-sheet manganese-lithium phosphate anode material of expanded graphite surface in situ growth.
Lithium ion battery is made in method same as Example 1, and electro-chemical test shows in 0.2C, 2.0-4.5V voltage
First discharge specific capacity is 110mAh/g in range；Capacity retention ratio is after/200 circulations under the conditions of 1C, 2.0-4.5V
85%, under 0.2C, 0.5C, 1C, 2C, 5C, 10C, 20C, 30C multiplying power, specific discharge capacity be respectively 110.4mAh/g,
102mAh/g, 90mAh/g, 72mAh/g, 51mAh/g, 34mAh/g, 22mAh/g and 3mAh/g, in contrast on expanded graphite surface
The chemical property of the nano-sheet manganese-lithium phosphate anode material of growth in situ, it was demonstrated that contained using expanded graphite surface with part
The characteristics of oxygen functional group, carries out solvent thermal reaction in combination with the organic solvent for having hydroxyl, so that having (020) advantage brilliant
Have between particle and particle prepared by the method that the manganese phosphate lithium nanosheet in face is grown in expanded graphite surface in situ good
Dispersibility, and the manganese-lithium phosphate anode material being in contact in such a way that surface-to-surface is in contact with expanded graphite, have excellent
Stable circulation performance and high rate performance.
It is enlightenment with the above-mentioned desirable embodiment according to the application, through the above description, relevant staff is complete
Full various changes and amendments can be carried out in the range of without departing from this item application technical idea.The technology of this item application
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of preparation method of nano-sheet manganese phosphate anode material for lithium-ion batteries characterized by comprising
Expanded graphite is added in the solvent containing alcohol type organic, lithium salts is dissolved in wherein, is configured to solution A, wherein solution A
Middle lithium concentration be 0.1-3.5mol/L, elemental lithium, expanded graphite mass ratio be 0.45-2.3: 1；
Phosphorus source is dissolved in the solution B for being configured to that phosphate concentration is 0.03-2.6mol/L in the solvent containing alcohol type organic, it will
Solution B is added in solution A is configured to solution C under agitation, wherein the solvent volume of the solvent of solution B and solution A ratio
It is 0.4-0.8: 1；
Manganese source is dissolved in the solution D that manganese ion concentration 0.025-2.2mol/L is made into alcohol type organic and water mixed solvent；
Solution D is mixed with solution C under stirring conditions, wherein the solvent volume of the solvent of solution D and solution A ratio is 0.5-
1.0: 1, and controlling reaction temperature is 140-220 DEG C, products therefrom is filtered and is used in combination after the reaction was completed by reaction time 6-20h
Alcohols and deionized water are washed repeatedly, until filtrate pH value is 6-7, obtain precursor powder after dry；
After precursor powder is mixed with carbon source, it is warming up to 400-900 DEG C under a shielding gas, it is cold with furnace after keeping the temperature the 2-8h time
But to room temperature to get to the nano-sheet manganese-lithium phosphate anode material that is grown in expanded graphite surface in situ.
2. preparation method according to claim 1, which is characterized in that the expanded graphite is being protected by graphite oxide
It is obtained under gas in 400-900 DEG C of calcining 1-4h；
The expanded graphite, which is added in solvent, passes through ultrasonication 1h or more.
3. preparation method according to claim 2 or 3, which is characterized in that it is described containing alcohol type organic solvent be ethyl alcohol
Or the mixture of ethylene glycol or ethyl alcohol, ethylene glycol and deionized water.
4. preparation method according to claim 1-3, which is characterized in that the manganese source be manganese sulfate, manganese acetate,
At least one of manganese nitrate.
5. preparation method according to claim 1-3, which is characterized in that phosphorus source is phosphoric acid, biphosphate
At least one of ammonium.
6. preparation method according to claim 1-3, which is characterized in that the carbon source is sucrose, glucose, more
At least one of bar amine, polypyrrole, phenolic resin, cetyl trimethylammonium bromide, polyvinylpyrrolidone.
7. preparation method according to claim 1-3, which is characterized in that the lithium salts is lithium acetate, hydroxide
At least one of lithium, lithium carbonate.
8. preparation method according to claim 1-3, which is characterized in that after precursor powder is mixed with carbon source,
The heating rate of heating is 2-6 DEG C/min.
9. preparation method according to claim 2, it is characterised in that: the protective gas be nitrogen, argon gas or nitrogen with
The mixed gas or argon gas of hydrogen and the mixed gas of hydrogen；In the mixed gas of the nitrogen and hydrogen, nitrogen accounts for 80~
99V%, hydrogen account for 1~20V%；In the mixed gas of the argon gas and hydrogen, argon gas accounts for 80~99V%, and hydrogen accounts for 1~
20V%.
10. a kind of nano-sheet manganese phosphate anode material for lithium-ion batteries, which is characterized in that by any one of claim 1-9 institute
The preparation method stated is prepared.
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| CN102544484A (en) * | 2011-05-12 | 2012-07-04 | 中国科学院福建物质结构研究所 | Lamellar manganese lithium phosphate (LiMnPO4) nano-crystal with high-proportion 020 crystal face and method for preparing lamellar LiMnPO4 nano-crystal |
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| US8691441B2 (en) * | 2010-09-07 | 2014-04-08 | Nanotek Instruments, Inc. | Graphene-enhanced cathode materials for lithium batteries |
| CN102544484A (en) * | 2011-05-12 | 2012-07-04 | 中国科学院福建物质结构研究所 | Lamellar manganese lithium phosphate (LiMnPO4) nano-crystal with high-proportion 020 crystal face and method for preparing lamellar LiMnPO4 nano-crystal |
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