CN105810911B - A kind of preparation method of high magnification lithium ferric phosphate/grapheme composite positive electrode material - Google Patents
A kind of preparation method of high magnification lithium ferric phosphate/grapheme composite positive electrode material Download PDFInfo
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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
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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
- 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
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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
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
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- 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
Abstract
The present invention relates to a kind of preparation methods of lithium ferric phosphate/grapheme composite positive electrode material, mainly obtain LiFePO4/graphene complex by the step solvent thermal reaction that polymer assists.The preparation method includes: that (1) disperses graphene and auxiliary polyalcohol in a solvent, it is made into suspension, phosphoric acid, lithium hydroxide are each configured to solution, and phosphoric acid is sequentially added dropwise into suspension, and the solution of lithium hydroxide obtains adhering to lithium phosphate suspension on the surface of graphene；(2) soluble ferrite and antioxidant are added in Xiang Shangshu suspension, is then transferred into reaction kettle and carries out solvent thermal reaction；(3) compound is obtained after separation, washing, drying to mix with organic carbon source, obtain LiFePO4-grapheme composite positive electrode material after high-temperature heat treatment under an inert atmosphere.It is sufficiently compound that LiFePO4 and graphene in composite positive pole are obtained by this method, and material has fabulous high rate performance, can be used in lithium ion power battery cathode material.
Description
Technical field
The invention belongs to field of lithium ion battery anode, and in particular to a kind of high magnification LiFePO4/graphene is multiple
The preparation method of positive electrode is closed, gained lithium ferric phosphate/grapheme composite positive electrode material has high high rate performance, can answer extensively
For lithium-ion-power cell material.
Background technique
Lithium ion battery is the energy storage device of a new generation, has that energy density is high, have extended cycle life, self discharge is small, without note
The advantages that recalling effect is had been widely used at present in portable electronic products such as laptop, mobile phone, digital cameras.Lithium-ion electric
Pond is made of anode, cathode, diaphragm and electrolyte, and wherein positive electrode plays decisive role to battery performance.It uses at present
Positive electrode include layer structure LiCoO2, spinel structure LiMnO2And the LiFePO of olivine structural4Deng.
With LiCoO2And LiMnO2It compares, LiFePO4Theoretical specific capacity (170 mAh/g) with higher, excellent circulation
The advantages that stability, high high-temp stability and low in cost, non-environmental-pollution, but its high rate performance and cryogenic property are opposite
It is poor.On the one hand the reason of causing these problems is LiFePO4Self-conductive poor (~ 10-9S/cm), on the other hand
LiFePO4Crystal structure has apparent anisotropy, and lithium ion can only be spread by the one-dimensional channel migration along b axis direction
Weaker (the LiFePO at room temperature of ability4Middle lithium ion mobility rate is 1.8 × 10-14 cm2/ S, FePO4Middle lithium ion mobility rate
It is 2.2 × 10-16 cm2/ S).These seriously limit LiFePO4The application of lithium ion battery.
By regulating and controlling LiFePO4Lithium ion diffusion rate can be improved in the size and shape of particle, to realize LiFePO4
The performance improvement of lithium ion battery.Patent CN101007630A discloses a kind of LiFePO of controllable pattern4Preparation method is led to
Sub-micron, nanoscale LiFePO can be prepared in the solvent thermal reaction for crossing addition crystal growth inhibitor4Particle.Patent
CN101327920A discloses a kind of flake LiFePO4There is nanocrystalline powder and preparation method thereof (020) to be orientated
Laminar LiFePO4It is nanocrystalline, conducive to the abjection and insertion of lithium ion in crystal.However as LiFePO4Particle size reduces,
The volume energy density of one side battery can reduce (bulk density reduction), on the other hand but also LiFePO4Particle and afflux
Electric conductivity, caking property are deteriorated between body, need using more conductive agents and binder.
Graphene is the two dimensional crystal being made of the carbon atom of sp2 hydridization, has good electric conductivity, big specific surface
Product.The excellent electric property of graphene makes it suitable as conductive additive.Patent CN101794874A is disclosed with graphene
For the electrode of conductive additive and the application in lithium ion battery, anode is prepared by directly adding graphene conductive agent
Piece, high-power charge-discharge performance, efficiency for charge-discharge and the cycle life of battery are all significantly improved.Patent
CN101752561A passes through graphene and LiFePO4Particle is mixed to get the mode of compound to improve battery performance, but directly
Mixing is so that LiFePO4Particle is weaker in conjunction with graphene, not can avoid the reunion of graphene itself.Patent
CN102044666A, CN102104143A, CN102299326A, CN103094564A and CN104779395A etc. pass through solvent heat
Method growth in situ LiFePO on the surface of graphene4It is poly- not can solve graphene itself under high-temperature solvent heat condition equally for particle
The problem of collection.Patent CN102751496A passes through preparation Fe2O3/ graphene complex is then anti-by solvent heat as presoma
It should obtain LiFePO4/ graphene complex, however its process is comparatively laborious.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of high magnification lithium ferric phosphate/grapheme composite positive electrode material, should
Method can be realized LiFePO4It is abundant compound with graphene, obtained lithium ferric phosphate/grapheme composite positive electrode material have compared with
High high rate performance.Specific step is as follows:
(1) graphene and auxiliary polyalcohol are dispersed in a solvent, graphene dispersing solution to be obtained, by phosphoric acid and lithium hydroxide
Wiring solution-forming respectively；Phosphoric acid solution, lithium hydroxide solution is added dropwise respectively into graphene dispersing solution, formation is attached to graphene table
The lithium phosphate suspension in face；The mass ratio of auxiliary polyalcohol and graphene is (0.5 ~ 3): 1；Phosphoric acid is with graphene mass ratio
(10 ~ 100): 1, the molar ratio of lithium hydroxide and phosphoric acid is (2.5 ~ 3): 1；
(2) Xiang Shangshu, which is attached in the lithium phosphate suspension of graphene surface, is added soluble ferrite and antioxidant,
It is then transferred into solvent thermal reaction kettle and reacts, obtain adhering to LiFePO4 solution on the surface of graphene；It is anti-to control solvent heat
Answering temperature is 140 ~ 200 DEG C, and the reaction time is 0.5 ~ 20 hour；Mole of phosphoric acid described in soluble ferrite and step (1)
Than for 1:1；
(3) product that step (2) obtains passed through into separation, wash and obtains LiFePO4/graphene after dry and is compound
Object mixes gained LiFePO4/graphene complex with organic carbon source, obtains phosphorus after high-temperature heat treatment under an inert atmosphere
Sour iron lithium/grapheme composite positive electrode material.
In the present invention, the graphene is the single layer removed by graphite or few layer graphene.
In the present invention, the auxiliary polyalcohol is the polymer that can receive proton forming salt, for linear (branching) poly- second
It is any in alkene imines or polyacrylamide.
In the present invention, solvent described in step (1) is the mixed solvent of water and alcohol.
In the present invention, the alcohol is ethylene glycol or glycerine, and the volume ratio of water and alcohol is 1:0.1 ~ 10.
In the present invention, the soluble ferrite is ferrous sulfate, frerrous chloride, ferrous acetate and its corresponding crystalline hydrate
It is any in object.
In the present invention, for the antioxidant to be any in L-AA, citric acid or glucose, dosage is solubility
0 ~ 20 wt% of ferrous salt quality.
In the present invention, to be any in glucose, sucrose, polystyrene or phenolic resin, dosage is the organic carbon source
0 ~ 20 wt% of LiFePO4/graphene complex quality.
In the present invention, high-temperature heat treatment temperature described in step (3) is 550 ~ 750 DEG C, and heat treatment time is 1 ~ 10 hour.
The present invention utilizes auxiliary polyalcohol and H3PO4Reaction forms polyelectrolyte and is adsorbed onto graphene surface, then with LiOH
Reaction forms Li on the surface of graphene3PO4Precipitating hinders self aggregation of graphene under the conditions of solvent heat, while being conducive in situ
Grow LiFePO4Particle.Auxiliary polyalcohol decomposition further makes LiFePO in the hot situation of high-temperature water4Particle is sufficiently tied with graphene
It closes.
The present invention obtains the LiFePO of size uniformity by solvent thermal reaction4Nanometer sheet has excellent lithium ion mobility
Performance, in combination with the excellent electric conductivity of graphene and LiFePO4Nanometer sheet and graphene it is abundant compound, what is obtained is compound
Material has high high rate performance, has wide practical use in lithium-ion-power cell field.
Detailed description of the invention
Fig. 1 is LiFePO4/graphene complex XRD spectrum that embodiment 1 obtains.
Fig. 2 is the XRD spectrum for the compound that embodiment 2 obtains.
Fig. 3 is the XRD spectrum for the LiFePO4 that embodiment 3 obtains.
Fig. 4 is LiFePO4/graphene complex FESEM figure that embodiment 1 obtains.
Fig. 5 is the FESEM figure for the compound that embodiment 2 obtains.
Fig. 6 is the FESEM figure for the LiFePO4 that embodiment 3 obtains.
Fig. 7 is that the rate discharge curves that battery testing obtains are made in 1 composite positive pole of embodiment.
Fig. 8 is that the circulation discharge curve obtained under 10 C multiplying power test condition of battery is made in 1 composite positive pole of embodiment.
Fig. 9 is that the rate discharge curves that battery testing obtains are made in 2 compound of embodiment.
Figure 10 is that the rate discharge curves that battery testing obtains are made in 3 LiFePO4 of embodiment.
Figure 11 is that the rate discharge curves that battery testing obtains are made in 4 composite positive pole of embodiment.
Specific embodiment
The present invention is further elaborated in the following with reference to the drawings and specific embodiments.Following embodiment be intended to the present invention into
Row explanation, does not do any restriction to summary of the invention itself.It should be understood that the one or more steps that the present invention mentions is not repelled
It is other there is also that can also be inserted between other method and steps or these specifically mentioned steps before and after the combination step
Method and steps.It should also be understood that these examples are only illustrative of the invention and is not intended to limit the scope of the invention.Unless otherwise
Illustrate, the number of various method steps be only identify the purpose of various method steps, rather than for limit the arrangement order of each method or
Practical range of the invention is limited, relativeness is altered or modified, under conditions of no substantial technological content alteration, when also
It is considered as the enforceable scope of the present invention.
Embodiment 1
60 mL ethylene glycol and 20 mL deionized waters are made into mixed solvent, and 60 mg graphene dispersions is taken to mix to 30 mL
In solvent, the branched polyethylene imine PEI that 60 mg molecular weight are 600 is added thereto, ultrasound 30 minutes is dripped dropwise under stirring
Add the H of 1.46 g 85%3PO4The solution being dissolved in 10 mL solvents drips off stirring 30 minutes, obtains mixed liquor A.Configure 1.44 g
LiOH·H2O is dissolved in the solution B of 30 mL solvents.Mixed liquor A is gradually dropped in solution B, and residual solvent is added, stirring 30
3.52 g FeSO are rapidly added after minute4·7H2O and 0.40 g L-AA.Closed stirring was transferred to solvent heat after 30 minutes
In reaction kettle, in 200 DEG C of 12 h of reaction.After cooling, respectively three times with deionized water and ethanol washing, it is centrifugated, it is dry.?
To powder mixed with the glucose of 20 wt% after in the sealing tube furnace of nitrogen protection 700 DEG C be sintered 5 hours, obtain phosphoric acid
Iron lithium/graphene complex.
LiFePO4 can be seen that by powder x-ray diffraction as olivine structural in resulting compound, such as Fig. 1 institute
Show.Field emission scanning electron microscope (FESEM) shows that LiFePO4 attachment is on the surface of graphene in compound, the size of particle
Length and width nanometers up to a hundred, thickness is at tens nanometers, as shown in Figure 4.Obtained compound is made into CR2016 battery, positive group becomes
Active material: conductive agent SP: binder PVDF=8:1:1, using metal lithium sheet as cathode.Test voltage range 2.5-3.8 V, temperature
25 DEG C of degree.Fig. 7 gives its rate discharge curves, has the specific capacity of 153 high mAh/g in the case of 0.2 C of low range, with
Multiplying power increase, 10 C have 138 mAh/g specific capacity, 20 C specific capacities be 135 mAh/g, be equivalent to and be able to maintain low power
The capacity of 88 % when rate.There is under the conditions of high magnification preferable cyclical stability, discharge cycles such as Fig. 8 under 10 C multiplying powers simultaneously
It is shown, the capacity of 96 % can be retained after 300 circulations.
Embodiment 2
60 mL ethylene glycol and 20 mL deionized waters are made into mixed solvent, and 60 mg graphene dispersions is taken to mix to 30 mL
In solvent, the branched polyethylene imine PEI that 60 mg molecular weight are 600, ultrasound 30 minutes are added thereto.1.44 g are added
LiOH·H2O is dissolved in the solution of the mixed solvent of 30 mL, is uniformly mixed.It is added dropwise 1.46 g's 85% under stirring dropwise
H3PO4It is dissolved in the solution of 10 mL in the mixed solvents, and residual solvent is added, stirring was rapidly added 3.52 g after 30 minutes
FeSO4·7H2O and 0.40 g L-AA.Closed stirring is transferred in solvent thermal reaction kettle after 30 minutes, is reacted at 200 DEG C
12 h.After cooling, respectively three times with deionized water and ethanol washing, it is centrifugated, it is dry.The Portugal of obtained powder and 20 wt%
Grape sugar mixing after in the sealing tube furnace of nitrogen protection 700 DEG C be sintered 5 hours, it is compound to be similarly obtained LiFePO4/graphene
Object.
The X-ray diffractogram of compound is as shown in Figure 2.Field emission scanning electron microscope is as shown in Figure 5.As a comparison
Example, compared with Example 1, graphene are not that very closely, can separate both in centrifugal separation processes in conjunction with LiFePO4, from
FESME is upper it is also seen that the LiFePO4 of graphene surface is than more loose.Obtained compound is made into CR2016 battery, item
For part with embodiment 1, Fig. 9 gives its rate discharge curves.Specific capacity is 80mAh/g when 10 C, and specific capacity is 65 when 20 C
MAh/g, performance obtain the good of compound not as good as embodiment 1.
Embodiment 3
60 mL ethylene glycol and 20 mL deionized waters are made into mixed solvent.By 1.44 g LiOHH2O is dissolved in 30 mL's
In the mixed solvent.The H of 1.46 g 85% is added dropwise under stirring dropwise3PO4It is dissolved in the solution of 10 mL in the mixed solvents, and residue is added
Solvent, stirring were rapidly added 3.52 g FeSO after 30 minutes4·7H2O and 0.40 g L-AA.Closed stirring 30 minutes
After be transferred in solvent thermal reaction kettle, in 200 DEG C of 12 h of reaction.After cooling, respectively three times with deionized water and ethanol washing, centrifugation
Separation, it is dry.700 DEG C of sintering 5 in the sealing tube furnace of nitrogen protection after obtained powder is mixed with the glucose of 20 wt%
Hour, obtain LiFePO4.
The X-ray diffractogram of LiFePO4 is as shown in Figure 3.Field emission scanning electron microscope is as shown in Figure 6.As a comparison
Example, Figure 10 give its rate discharge curves.Specific capacity is 97mAh/g when 10 C, and specific capacity is 84 mAh/g when 20 C.With reality
It applies example 1 to compare, LiFePO4/graphene complex obtained promotes high rate performance apparent.
Embodiment 4
For step with embodiment 1, glucose additive amount is 10 wt% of powder.Rate discharge curves are as shown in figure 11.Pass through
Improve carbon content, the performance of compound is further obviously improved, and specific capacity is 148mAh/g when 10 C, and specific capacity is when 20 C
142 mAh/g。
Claims (8)
1. a kind of preparation method of high magnification lithium ferric phosphate/grapheme composite positive electrode material, which is characterized in that pass through hydro-thermal reaction
The laminar LiFePO4 of nano-scale is prepared in situ out on the surface of graphene, the specific steps are as follows:
(1) graphene and auxiliary polyalcohol are dispersed in a solvent, to obtain graphene dispersing solution, phosphoric acid and lithium hydroxide is distinguished
Wiring solution-forming；Phosphoric acid solution, lithium hydroxide solution is successively added dropwise respectively into graphene dispersing solution, formation is attached to graphene table
The lithium phosphate suspension in face；The mass ratio of auxiliary polyalcohol and graphene is (0.5 ~ 3): 1；Phosphoric acid is with graphene mass ratio
(10 ~ 100): 1, the molar ratio of lithium hydroxide and phosphoric acid is (2.5 ~ 3): 1；The auxiliary polyalcohol is that can receive proton to be formed
The polymer of salt is any in L-PEI, branched polyethylene imine or polyacrylamide；
(2) Xiang Shangshu, which is attached in the lithium phosphate suspension of graphene surface, is added soluble ferrite and antioxidant, then
It is transferred in solvent thermal reaction kettle and reacts, obtain adhering to LiFePO4 solution on the surface of graphene；Control solvent thermal reaction temperature
Degree is 140 ~ 200 DEG C, and the reaction time is 0.5 ~ 20 hour；Soluble ferrite and the molar ratio of phosphoric acid described in step (1) are
1:1；
(3) product that step (2) obtains is obtained into LiFePO4/graphene complex after separation, washing and drying, it will
Gained LiFePO4/graphene complex is mixed with organic carbon source, obtains ferric phosphate after high-temperature heat treatment under an inert atmosphere
Lithium/grapheme composite positive electrode material.
2. preparation method according to claim 1, which is characterized in that the graphene is the list removed by graphite
Layer or few layer graphene.
3. preparation method according to claim 1, which is characterized in that solvent described in step (1) is the mixing of water and alcohol
Solvent.
4. preparation method according to claim 3, which is characterized in that the alcohol is ethylene glycol or glycerine, water and alcohol
Volume ratio is 1:0.1 ~ 10.
5. preparation method according to claim 1, which is characterized in that the soluble ferrite is ferrous sulfate, chlorination
It is any in ferrous, ferrous acetate and its corresponding crystalline hydrate.
6. preparation method according to claim 1, which is characterized in that the antioxidant is L-AA, citric acid
Or it is any in glucose, dosage is 0 ~ 20wt% of soluble ferrite quality.
7. preparation method according to claim 1, which is characterized in that the organic carbon source is glucose, sucrose, polyphenyl second
Any in alkene or phenolic resin, dosage is 0 ~ 20wt% of LiFePO4/graphene complex quality.
8. preparation method according to claim 1, which is characterized in that high-temperature heat treatment temperature described in step (3) is 550
~ 750 DEG C, heat treatment time is 1 ~ 10 hour.
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| CN106410168B (en) * | 2016-12-07 | 2019-05-14 | 中南大学 | LiFePO4/graphene composite material and preparation method thereof that nano flake stacks |
| CN106848247A (en) * | 2017-03-01 | 2017-06-13 | 桂林理工大学 | Method based on ferric phosphate Hydrothermal Synthesiss high-performance iron phosphate lithium/three-dimensional porous graphene composite material |
| CN108199019A (en) * | 2017-12-25 | 2018-06-22 | 深圳市山木新能源科技股份有限公司 | Multi-layer graphene/LiFePO4 intercalation composite material preparation method and application |
| CN114583123A (en) * | 2022-02-17 | 2022-06-03 | 宜都兴发化工有限公司 | Phosphorus-doped carbon-coated ultrathin lithium iron phosphate lamellar material and preparation method thereof |
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| CN103904325A (en) * | 2014-03-21 | 2014-07-02 | 天津大学 | High-multiplying-power type lithium iron phosphate/carbon composite material and preparation method thereof |
| CN104393265A (en) * | 2014-12-04 | 2015-03-04 | 张桂萍 | Preparation method of interface strong coupling graphene-lithium iron phosphate nano-composite positive electrode material |
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| CN104393265A (en) * | 2014-12-04 | 2015-03-04 | 张桂萍 | Preparation method of interface strong coupling graphene-lithium iron phosphate nano-composite positive electrode material |
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