CN107068990A - Graphene composite lithium iron phosphate cathode material and preparation method and application - Google Patents
Graphene composite lithium iron phosphate cathode material and preparation method and application 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
- H01M4/364—Composites as mixtures
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
Abstract
The invention discloses a kind of graphene composite lithium iron phosphate cathode material and preparation method and application.The graphene composite lithium iron phosphate cathode material includes the aggregation and dispersed graphene of LiFePO4 second particle, and the graphene coated is on LiFePO4 second particle and is distributed between LiFePO4 second particle；And its preparation method includes：Lithium source, source of iron, phosphorus source, carbon source are mixed with sulfonated graphene, presoma is formed；By the presoma in an inert atmosphere in being calcined under high temperature, cool down afterwards, the graphene composite lithium iron phosphate cathode material is made.The graphene composite lithium iron phosphate cathode material that the present invention is provided has excellent electric conductivity, high rate performance, cycle performance and cryogenic property etc.; the multinomial performance of lithium ion battery can be greatly improved when applied to lithium ion battery; the preparation technology of the graphene composite lithium iron phosphate cathode material is simply controllable simultaneously; it is with low cost, beneficial to large-scale production.
Description
Technical field
The present invention relates to a kind of positive electrode that can be applied to lithium ion battery, particularly a kind of graphene compound phosphoric acid iron
Lithium anode material and preparation method and application.
Background technology
Lithium ion battery so that its operating voltage is high, energy density is high, is had extended cycle life, put certainly as new green power
Electric low, memory-less effect, it is pollution-free, unique advantage such as have a safety feature, be widely used in electric bicycle, electronic vapour
The fields such as car, electric bus, and progressively replacement is passed in defence and military, space flight navigation, artificial satellite and military communication apparatus
The battery of system.The short more than ten years are developed rapidly, and occupation rate of the lithium ion battery in electrokinetic cell market is alreadyd exceed and portion
Divide and instead of traditional lead-acid battery and Ni-MH battery, be increasingly becoming the main flow of secondary cell.
Existing anode material for lithium-ion batteries is mainly cobalt acid lithium, LiMn2O4, LiFePO4, nickle cobalt lithium manganate etc..By
In the technical need of lithium-ion-power cell, LiFePO4 with its high security, long circulation life, good high-temperature stability and
The advantage such as with low cost, pollution-free, is widely used in power vehicle market.It is main but its high rate performance, cryogenic property are relatively poor
Reason is wanted to be that the electronic conductivity and lithium ionic mobility of LiFePO4 are low, which also limits the application of LiFePO4
Before this, researcher mainly improves the electric conductivity of LiFePO4, but this mode by the form of carbon doping, cladding
Performance to LiFePO4 improves limited.In recent years, if it was discovered by researchers that the addition of the materials such as graphene, CNT is existed
In LiFePO 4 material, the electric conductivity of LiFePO4 can be improved to a certain extent, but graphene, CNT are difficult uniform
It is dispersed in LiFePO 4 material, causes the electric conductivity of LiFePO4 unbalanced, in turn result in battery with two side terminals poor.
The content of the invention
It is a primary object of the present invention to provide a kind of graphene composite lithium iron phosphate cathode material and preparation method thereof with
Using to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The embodiments of the invention provide a kind of graphene composite lithium iron phosphate cathode material, it includes LiFePO4 and graphite
Alkene.
Further, in the graphene composite lithium iron phosphate cathode material, based on graphene uniform is dispersed in
In the LiFePO4 of component.
Further, in the graphene composite lithium iron phosphate cathode material content of graphene be preferably 0.05wt%~
10wt%, especially preferably 0.1wt%~3wt%.
Further, the piece footpath average-size of the graphene is preferably 100nm~200 μm, and especially preferably 500nm~
100μm。
Further, the thickness of the graphene is preferably 1nm~20nm, especially preferably 1nm~5nm.
Further, the aggregation of the graphene composite lithium iron phosphate cathode material including LiFePO4 second particle and
Dispersed graphene, which part graphene coated is on LiFePO4 second particle, and part graphene uniform is scattered in
Between LiFePO4 second particle.
Further, the particle diameter D50 of the LiFePO4 second particle is between 0.5 μm~5 μm.
Further, the tap density of the graphene composite lithium iron phosphate cathode material is 0.8g/cm3~1.5g/
cm3, specific surface area is 10m2/ g~20m2/ g, resistivity is the Ω of 1 Ω cm~100 cm, and 0.1C grams of specific capacity is 155mAh/g
~165mAh/g.
The embodiment of the present invention additionally provides a kind of preparation method of graphene composite lithium iron phosphate cathode material.
In some embodiments, the preparation method includes：Sulfonated graphite aqueous solution is added to before LiFePO4
Drive in somaplasm material and mix, be ground with sand mill, granularity is ground to after certain particle size and is dried, and prepares compound precursor
Body, then roasting obtains graphene composite lithium iron phosphate cathode material under an inert atmosphere.
In some more specific embodiment, the preparation method may also include：
Lithium source, source of iron, phosphorus source, carbon source are mixed with sulfonated graphene, presoma is formed；
The presoma is incubated 2~8h in 600 DEG C~800 DEG C in an inert atmosphere, cools down afterwards, the graphite is made
Alkene composite lithium iron phosphate cathode material.
In some more specific embodiment, described preparation method includes：
Lithium source, source of iron, phosphorus source, carbon source, sulfonated graphene and water are mixed to form in mixed material, the mixed material
Solid content is 20wt%~40wt%；
Processing is ground to the mixed material, the grain diameter D50 into mixed material is 100nm~300nm；
Polished mixed material is dried at 100~300 DEG C, the presoma is formed.
In some more specific embodiment, described preparation method includes：By lithium source, source of iron, phosphorus source, carbon source with
Sulfonated graphite aqueous solution is mixed to form the mixed material.
In some more specific embodiment, described preparation method includes：The mixed material is sanded
Processing, is sanded the time in more than 1h, the grain diameter D50 into mixed material is 100nm~300nm.
In some preferred embodiments, the lithium source, source of iron, the mol ratio of phosphorus source and carbon source are (1.02~1.10)：
1.0：(1.0~1.3)：(0.04~0.5).
Further, in the graphene composite lithium iron phosphate cathode material content of graphene be preferably 0.05wt%~
10wt%, especially preferably 0.1wt%~3wt%.
Further, the lithium source include lithium hydroxide, lithium carbonate, lithium phosphate, lithium dihydrogen phosphate in any one or
Two or more combinations, and not limited to this.
Further, the source of iron is included in ferric phosphate, ferrous oxalate, di-iron trioxide, ferric sulfate, ferroso-ferric oxide
Any one or two or more combinations, and not limited to this.
Further, phosphorus source includes any one in phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate
Plant or two or more combinations, and not limited to this.
Further, the carbon source includes any one in sucrose, glucose, phenolic resin, citric acid, carbon black or two
Plant the combination of the above, and not limited to this.
Further, foregoing water and the water as solvent in sulfonated graphite aqueous solution are preferably pure water, gone
Ionized water etc., and not limited to this.
Further, the piece footpath of the sulfonated graphene, thickness and element composition can be as it was noted above, no longer go to live in the household of one's in-laws on getting married herein
State.
The embodiment of the present invention additionally provides the graphene composite lithium iron phosphate cathode material prepared by methods described.
The embodiment of the present invention additionally provides the purposes of the graphene composite lithium iron phosphate cathode material, for example, preparing lithium
Purposes in ion battery.
Compared with prior art, the graphene composite lithium iron phosphate cathode material that the present invention is provided has excellent conduction
Property, high rate performance, cycle performance and cryogenic property etc., many of lithium ion battery can be greatly improved when applied to lithium ion battery
Item performance, while the preparation technology of the graphene composite lithium iron phosphate cathode material is simply controllable, it is with low cost, beneficial to scale
Metaplasia is produced.
Brief description of the drawings
Fig. 1 is a kind of SEM figures of graphene composite lithium iron phosphate cathode material in the embodiment of the present invention 1.
Fig. 2 be in the embodiment of the present invention 1 a kind of graphene composite lithium iron phosphate cathode material in the circulation of 0.1C-5C multiplying powers
Volume test figure.
Fig. 3 be in the embodiment of the present invention 1 a kind of graphene composite lithium iron phosphate cathode material in the circulation volume of 1C multiplying powers
Test chart.
Fig. 4 is a kind of LFP resistivity measurement figures of graphene composite lithium iron phosphate cathode material in the embodiment of the present invention 1；
Fig. 5 is a kind of cryogenic property test chart of graphene composite lithium iron phosphate cathode material in the embodiment of the present invention 1；
Fig. 6 is a kind of graphite in a kind of graphene composite lithium iron phosphate cathode material and reference examples 2 in the embodiment of the present invention 1
The charge/discharge capacity test chart of alkene composite lithium iron phosphate cathode material.
Embodiment
In view of deficiency of the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical scheme.To combine as follows some embodiments and accompanying drawing technical scheme, its implementation process and principle etc. will be made into
The explanation of one step.
Following examples are related to a series of preparation technology of graphene composite lithium iron phosphate cathode materials, and it can be included such as
Lower step：
(1) it is (1.02~1.10) in molar ratio by lithium source, source of iron, phosphorus source, carbon source：1.0：(1.0~1.3)：(0.04~
0.5) (it is preferably (1.02~1.05)：1.0：(1.0~1.3)：(0.05~0.25)) weigh, the material weighed is put into batch mixing
In machine, while adding sulfonated graphene, (content of the final graphene in graphene composite lithium iron phosphate cathode material be
0.05wt%~10wt%, preferably 0.1wt%~3wt%), adjust solid content with pure water (excellent in 20wt%~40wt%
Elect 25wt%~35wt% as), mix and progress more than sand milling 1h in sand mill (being preferably 1h~5h) is transferred to after 0.5h~2h, directly
Into mixed material, grain diameter D50 is 100nm~300nm；
(2) material after sand milling is dried 100 DEG C~300 DEG C (being preferably 200 DEG C~300 DEG C), dried pure
Water, obtains presoma；
(3) presoma is put into high temperature furnace, is passed through inert gas, 600~800 DEG C (being preferably 650 DEG C~750 DEG C)
2~8h (being preferably 4h~8h) is incubated, room temperature is cooled to；Obtain graphene composite lithium iron phosphate cathode material.
Foregoing lithium source may be selected from one or more of combinations of lithium hydroxide, lithium carbonate, lithium phosphate, lithium dihydrogen phosphate, and
Not limited to this.
Foregoing source of iron may be selected from ferric phosphate, ferrous oxalate, di-iron trioxide, ferric sulfate, one kind of ferroso-ferric oxide or several
The combination planted, and not limited to this.
Foregoing phosphorus source may be selected from one or more of groups of phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate
Close, and not limited to this.
Foregoing carbon source may be selected from one or more of combinations of sucrose, glucose, phenolic resin, citric acid, carbon black, and not
It is limited to this.
The piece footpath average-size of foregoing sulfonated graphene is 100nm~200 μm (being preferably 500nm~100 μm), and thickness is
1nm~20nm (being preferably 1nm~5nm), wherein C and S mol ratio are 12:1~6:1 (is preferably 8:1~6:1).
Embodiment 1：A kind of preparation technology of graphene composite lithium iron phosphate cathode material includes：Using lithium carbonate as lithium source,
Ferrous oxalate is source of iron, and ammonium dihydrogen phosphate is phosphorus source, and sucrose is carbon source, and lithium source, source of iron, phosphorus source, carbon source are pressed into 1.02：1.0：
1.0：0.1 mol ratio is weighed, and the material weighed is put into batch mixer, while sulfonated graphene and pure water are added, mixing
Progress sand milling 2h in sand mill is transferred to after 2h, until the grain diameter D50 in mixed material (solid content about 20wt%) is about
100nm；Material after sand milling is dried at a temperature of 200 DEG C, pure water is dried, obtains presoma；Presoma is put into
In high temperature furnace, inert gas is passed through, 5h is incubated at a temperature of 700 DEG C, is cooled to room temperature；Obtain graphene composite lithium iron phosphate just
Pole material.The SEM figures of the graphene composite lithium iron phosphate cathode material see Fig. 1, its resistivity measurement result such as Fig. 4 institutes
Show.According to GB31241-2014 to graphene composite lithium iron phosphate cathode material (LFP+ graphenes) made from the embodiment 1 and
Commercially available lithium iron phosphate positive material (LFP) is tested, and test result see shown in Fig. 2,3,5.
Embodiment 2：A kind of preparation technology of graphene composite lithium iron phosphate cathode material includes：By lithium hydroxide, phosphoric acid
Iron, phosphorus pentoxide and phenolic resin press 1.10：1.0：1.3：0.5 mol ratio is weighed, and the material weighed is put into batch mixer
In, while adding sulfonated graphene and deionized water, progress sand milling 1h in sand mill is transferred to after mixing 1h, until mixed material
Grain diameter D50 in (solid content about 40wt%) is about 300nm；Material after sand milling is dried at a temperature of 100 DEG C,
Deionized water is dried, presoma is obtained；Presoma is put into high temperature furnace, inert gas is passed through, is incubated at a temperature of 800 DEG C
2h, is cooled to room temperature；Obtain graphene composite lithium iron phosphate cathode material.
Embodiment 3：A kind of preparation technology of graphene composite lithium iron phosphate cathode material includes：By lithium dihydrogen phosphate, four
Fe 3 O, diammonium hydrogen phosphate and citric acid press 1.05：1.10：1.0：0.04 mol ratio is weighed, and the material weighed is put into
In batch mixer, while adding sulfonated graphene and deionized water, progress sand milling 1.5h in sand mill is transferred to after mixing 0.5h, until
Grain diameter D50 in mixed material (solid content about 25wt%) is about 200nm；By the material after sand milling at a temperature of 300 DEG C
It is dried, dries deionized water, obtain presoma；Presoma is put into high temperature furnace, inert gas is passed through, in 750 DEG C of temperature
The lower insulation 6h of degree, is cooled to room temperature；Obtain graphene composite lithium iron phosphate cathode material.
Embodiment 4：A kind of preparation technology of graphene composite lithium iron phosphate cathode material includes：By lithium phosphate, ferric sulfate,
Phosphoric acid and carbon black press 1.03：1.0：1.3：0.25 mol ratio is weighed, and the material weighed is put into batch mixer, while adding sulphur
Progress sand milling 5h in sand mill is transferred to after graphite alkene and deionized water, mixing 1.5h, (solid content is about up to mixed material
Grain diameter D50 in 30wt%) is about 100nm；Material after sand milling is dried at a temperature of 250 DEG C, drying go from
Sub- water, obtains presoma；Presoma is put into high temperature furnace, inert gas is passed through, 8h is incubated at a temperature of 650 DEG C, is cooled to
Room temperature；Obtain graphene composite lithium iron phosphate cathode material.
Embodiment 5：A kind of preparation technology of graphene composite lithium iron phosphate cathode material includes：By lithium phosphate, three oxidations
Two iron, phosphoric acid and sucrose press 1.05：1.0：1.1：0.05 mol ratio is weighed, and the material weighed is put into batch mixer, simultaneously
Progress sand milling 3h in sand mill is transferred to after adding sulfonated graphene and deionized water, mixing 1.5h, until mixed material (solid content
About 35wt%) in grain diameter D50 be about 150nm；Material after sand milling is dried at a temperature of 250 DEG C, drying is gone
Ionized water, obtains presoma；Presoma is put into high temperature furnace, inert gas is passed through, 4h is incubated at a temperature of 700 DEG C, is cooled down
To room temperature；Obtain graphene composite lithium iron phosphate cathode material.
Likewise, with reference to embodiment 1, to graphene composite lithium iron phosphate made from foregoing embodiment 2- embodiments 5 just
The pattern and performance of pole material are tested, and also can obtain similar characterization result.
To sum up it can be seen that, the graphene composite lithium iron phosphate cathode material that provides of the present invention have excellent electric conductivity,
High rate performance, cycle performance and cryogenic property etc., the multinomial of lithium ion battery can be greatly improved when applied to lithium ion battery
Performance.
Reference examples 1：The reference examples 1 are substantially the same manner as Example 1, but are not added with foregoing sulfonated graphene.
Reference examples 2：The reference examples 2 are substantially the same manner as Example 1, but the graphite oxide prepared with hummers methods purchased in market
Alkene instead of foregoing sulfonated graphene.
Likewise, with reference to embodiment 1, to the graphene composite lithium iron phosphate prepared by foregoing reference examples 1, reference examples 2 just
Electric conductivity, high rate performance, cycle performance and cryogenic property of pole material etc. are tested, and are as a result shown, comparative example 2 obtains stone
Electric conductivity of black alkene composite lithium iron phosphate cathode material etc. has small elevation than comparative example 1, but the remote embodiment 1- that is inferior to is implemented
The obtained product of example 5, meanwhile, comparative example 2 obtains the cryogenic property of graphene composite lithium iron phosphate cathode material than comparative example 1 simultaneously
Without significant changes, the obtained product of embodiment 1- embodiments 5 (referring to Fig. 6) is also far inferior to.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all
The equivalent change or modification made according to spirit of the invention, should all be included within the scope of the present invention.
Claims (10)
1. a kind of graphene composite lithium iron phosphate cathode material, it is characterised in that include LiFePO4 and graphene；It is preferred that, institute
The content for stating graphene in graphene composite lithium iron phosphate cathode material is 0.05wt%~10wt%, especially preferably
0.1wt%~3wt%；It is preferred that, the piece footpath average-size of the graphene is 100nm~200 μm, especially preferably 500nm
~100 μm；It is preferred that, the thickness of the graphene is 1nm~20nm, especially preferably 1nm~5nm.
2. graphene composite lithium iron phosphate cathode material according to claim 1, it is characterised in that：The graphene is combined
Lithium iron phosphate positive material includes the aggregation and dispersed graphene of LiFePO4 second particle, which part graphene
It is coated on LiFePO4 second particle, part graphene uniform is scattered between LiFePO4 second particle；It is preferred that, it is described
The particle diameter D50 of LiFePO4 second particle is between 0.5 μm~5 μm；It is preferred that, the graphene composite lithium iron phosphate positive pole material
The tap density of material is 0.8g/cm3~1.5g/cm3, specific surface area is 10m2/ g~20m2/ g, resistivity is 1 Ω cm~100
Ω cm, 0.1C grams of specific capacity is 155mAh/g~165mAh/g.
3. a kind of preparation method of graphene composite lithium iron phosphate cathode material, it is characterised in that including：
Lithium source, source of iron, phosphorus source, carbon source are mixed with sulfonated graphene, presoma is formed；
By the presoma, in 600 DEG C~800 DEG C (being preferably 650 DEG C~750 DEG C), 2~8h of insulation is (preferably in an inert atmosphere
For 4h~8h), cool down afterwards, the graphene composite lithium iron phosphate cathode material is made.
4. preparation method according to claim 3, it is characterised in that including：
Lithium source, source of iron, phosphorus source, carbon source, sulfonated graphene and water are mixed to form into consolidating in mixed material, the mixed material to contain
Measure as 20wt%~40wt%, preferably 25wt%~35wt%；
Processing is ground to the mixed material, the grain diameter D50 into mixed material is 100nm~300nm；
Polished mixed material is dried 100~300 DEG C (being preferably 200 DEG C~300 DEG C), the forerunner is formed
Body.
5. preparation method according to claim 4, it is characterised in that including：By lithium source, source of iron, phosphorus source, carbon source and sulfonation
Graphene aqueous solution is mixed to form the mixed material.
6. preparation method according to claim 4, it is characterised in that including：Sanded treatment is carried out to the mixed material,
The sand milling time is 100nm~300nm in more than 1h, preferably 1h~5h, the grain diameter D50 into mixed material.
7. the preparation method according to any one of claim 3-5, it is characterised in that：The lithium source, source of iron, phosphorus source and carbon
The mol ratio in source is (1.02~1.10)：1.0：(1.0~1.3)：(0.04~0.5), be preferably (1.02~1.05)：1.0：
(1.0~1.3)：(0.05~0.25)；And/or, the content of graphene is in the graphene composite lithium iron phosphate cathode material
0.05wt%~10wt%, especially preferably 0.1wt%~3wt%.
8. the preparation method according to any one of claim 3-6, it is characterised in that：The lithium source include lithium hydroxide,
Any one in lithium carbonate, lithium phosphate, lithium dihydrogen phosphate or two or more combinations；And/or, the source of iron includes phosphoric acid
Any one in iron, ferrous oxalate, di-iron trioxide, ferric sulfate, ferroso-ferric oxide or two or more combinations；And/or, institute
Stating phosphorus source includes any one in phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or two or more combinations；
And/or, the carbon source includes any one or two or more groups in sucrose, glucose, phenolic resin, citric acid, carbon black
Close；And/or, the piece footpath average-size of the sulfonated graphene is 100nm~200 μm, preferably 500nm~100 μm；And/or,
The thickness of the sulfonated graphene is 1nm~20nm, preferably 1nm~5nm；And/or, C's and S rubs in the sulfonated graphene
You are than being 12:1~6:1, preferably 8:1~6:1.
9. graphene composite lithium iron phosphate cathode material prepared by the method as any one of claim 3-8.
10. graphene composite lithium iron phosphate cathode material described in claim 1,2 or 9 is in preparing the purposes in lithium ion battery.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417801A (en) * | 2018-03-07 | 2018-08-17 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of graphene In-situ reaction lithium iron phosphate positive material and preparation method thereof |
| CN110085809A (en) * | 2018-01-25 | 2019-08-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene nano tape base composite ferric lithium phosphate material, preparation method and application |
| CN110190275A (en) * | 2019-07-02 | 2019-08-30 | 宁夏汉尧石墨烯储能材料科技有限公司 | A kind of graphene modification lithium-ion battery tertiary cathode material |
| CN110723718A (en) * | 2019-10-31 | 2020-01-24 | 福州大学 | Preparation method of nitrogen-doped graphene/lithium iron phosphate composite material for lithium ion battery |
| CN112694078A (en) * | 2020-12-29 | 2021-04-23 | 陕西煤业化工技术研究院有限责任公司 | Graphene-coated lithium iron phosphate composite material and preparation method thereof |
| CN114784240A (en) * | 2022-04-11 | 2022-07-22 | 厦门海辰新能源科技有限公司 | Graphene-carbon-coated lithium iron phosphate positive electrode material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102412396A (en) * | 2011-11-11 | 2012-04-11 | 深圳市德方纳米科技有限公司 | Lithium ion battery electrode material coated with non-continuous graphene |
| US20150162610A1 (en) * | 2012-05-08 | 2015-06-11 | HYDRO-QUéBEC | Lithium-ion secondary battery and method of producing same |
| CN104993142A (en) * | 2015-05-25 | 2015-10-21 | 苏州高通新材料科技有限公司 | Sulfonated graphene lithium battery positive electrode additive and application thereof |
| CN105070911A (en) * | 2015-06-25 | 2015-11-18 | 中国航空工业集团公司北京航空材料研究院 | Lithium iron phosphate battery positive electrode material |
| CN105206802A (en) * | 2015-08-24 | 2015-12-30 | 苏州高通新材料科技有限公司 | Lithium-rich sulfonated graphene-nanometer SiOx negative electrode material and preparation method and application thereof |
-
2016
- 2016-12-26 CN CN201611218704.1A patent/CN107068990A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102412396A (en) * | 2011-11-11 | 2012-04-11 | 深圳市德方纳米科技有限公司 | Lithium ion battery electrode material coated with non-continuous graphene |
| US20150162610A1 (en) * | 2012-05-08 | 2015-06-11 | HYDRO-QUéBEC | Lithium-ion secondary battery and method of producing same |
| CN104993142A (en) * | 2015-05-25 | 2015-10-21 | 苏州高通新材料科技有限公司 | Sulfonated graphene lithium battery positive electrode additive and application thereof |
| CN105070911A (en) * | 2015-06-25 | 2015-11-18 | 中国航空工业集团公司北京航空材料研究院 | Lithium iron phosphate battery positive electrode material |
| CN105206802A (en) * | 2015-08-24 | 2015-12-30 | 苏州高通新材料科技有限公司 | Lithium-rich sulfonated graphene-nanometer SiOx negative electrode material and preparation method and application thereof |
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| CN108417801A (en) * | 2018-03-07 | 2018-08-17 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of graphene In-situ reaction lithium iron phosphate positive material and preparation method thereof |
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| CN114784240B (en) * | 2022-04-11 | 2023-09-22 | 厦门海辰储能科技股份有限公司 | Graphene-carbon coated lithium iron phosphate positive electrode material, and preparation method and application thereof |
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