CN103682251A - Porous ferric oxide/carbon nanometer plate composite material as well as preparation method thereof and application in preparing lithium ion battery - Google Patents
Porous ferric oxide/carbon nanometer plate composite material as well as preparation method thereof and application in preparing lithium ion battery Download PDFInfo
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- CN103682251A CN103682251A CN201310672536.3A CN201310672536A CN103682251A CN 103682251 A CN103682251 A CN 103682251A CN 201310672536 A CN201310672536 A CN 201310672536A CN 103682251 A CN103682251 A CN 103682251A
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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
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a porous ferric oxide/carbon nanometer plate composite material as well as a preparation method of the porous ferric oxide/carbon nanometer plate composite material and application in preparing a lithium ion battery. The method comprises the following steps of uniformly mixing raw materials including ferrocene and ammonium sulfate in a given mass ratio; calcining the mixture in an inert gas high-pressure reaction kettle, then calcining the mixture in the air at a low temperature to obtain the porous ferric oxide/carbon nanometer plate composite material. The preparation method is simple in process, easy to operate, high in yield and applicable to the mass production. When being used as a lithium ion battery cathode material, the prepared porous ferric oxide/carbon nanometer plate composite material is high in specific capacity and excellent in circulation stability, and the capacity of the material is more than 1000mAh/g after being circulated for 100 times.
Description
Technical field
The present invention relates to lithium ion battery field, particularly a kind of porous di-iron trioxide/carbon nanosheet composite material and preparation method thereof and the negative material and the lithium ion battery that use this material.
Background technology
Between the more than ten years in the past, Portable mobile electronic device has experienced the development of explosion type, notebook computer, and the various portable type electronic products such as digital camera are widely used, this provides more opportunities to develop for rechargeable secondary cell, has also proposed more requirements simultaneously.At present, along with the commercialized development of electric motor car of new generation and hybrid-power electric vehicle, the demand of high-capacity secondary battery increases day by day, the needs of environmental protection in addition, and people are devoted to tap a new source of energy more and more, to substituting the traditional energies such as coal and oil.In all secondary cells, lithium ion battery because thering is high power capacity, long circulation life, self discharge is little and the advantage such as high-energy-density, memory-less effect, greatly developed in recent years.As a kind of Typical Representative of novel energy, lithium ion battery has fairly obvious advantage, but also have, is much not enough to wait to improve simultaneously, and as high in cost, current commercialization electrode material capacity used is too low etc.Commercial Li-ion battery negative material used is mainly graphite-like material with carbon element at present.Because graphite-like material with carbon element intrinsic conductivity is high, Stability Analysis of Structures in removal lithium embedded process, have lower doff lithium current potential, and material with carbon element is less expensive, therefore in commercial applications, has a clear superiority in.But its theoretical capacity low (372 mAh/g), cannot meet the growing requirement to high power capacity, lithium ion battery with high energy density.Therefore, the lithium ion battery material of the high power capacity of development of new, long circulation and good rate capability is extremely urgent.At present; the new materials such as silicon, tin, transition metal oxide are counted as the potential substitution material of graphite cathode material; but also there is obvious defect in them; as large in the change in volume in doff lithium process; there is lower electronic conductivity; thereby exist larger irreversible capacity and stable circulation poor etc., this has also limited scale application of these new materials greatly.Negative material is the important component part of lithium ion battery, and its cycle performance quality has directly determined the useful life of lithium ion battery.Therefore, seek the preparation of simple method and have high power capacity and long-life negative material concurrently for producing high performance lithium ion battery, the application of widening lithium ion battery has extremely important realistic meaning.
Transition metal oxide, as Fe
2o
3, Fe
3o
4, CuO, CoO etc., because its higher theoretical capacity and preferably fail safe are subject to extensive concern in recent years.Yet transition metal oxide can produce larger change in volume in removal lithium embedded process, cause particle efflorescence, and oxide mostly is semiconductor, so conductivity is poor, thereby greatly reduces its cyclical stability.At present mainly by material nano and prepare composite material etc. transition metal oxide is carried out to modification.Material nanoization can significantly reduce efflorescence and the reunion that particle causes because of doff lithium process, can greatly improve the utilance of material.By compound with good material with carbon element of conductivity etc., can improve the electronic conductivity of metal oxide, the electrically contacting of reinforcing material integral body, the introducing of material with carbon element also can limit the efflorescence of particle greatly in addition.
Fe
2o
3the theoretical capacity as lithium ion battery negative material with 1007 mAh/g, approximately 2.7 times of graphite cathode material, in addition it also has the advantages such as with low cost, raw material source is abundant, safety and environmental protection, it is the lithium ion battery negative material that has prospect, yet cause particle efflorescence owing to can producing larger change in volume in its lower electronic conductivity and cyclic process, therefore its cyclical stability is poor, far below its theoretical capacity.After Chinese invention patent (publication No.: CN 102208614 A) utilizes molysite to be hydrolyzed in carbon source solution, calcining prepares the coated di-iron trioxide negative material of carbon, and this material has higher capacity and good cyclical stability.Chinese invention patent (publication No.: CN 102136565 A) is by magnetron sputtering deposition legal system for di-iron trioxide-selenium nano compound film, and this film has good stability as negative material.Above-mentioned patent, by different experiments method, has been improved the chemical property of di-iron trioxide, has shown the application prospect of di-iron trioxide aspect lithium ion battery negative material.
Two-dimensional nano sheet composite material is study hotspot in recent years.In lithium ion battery applications, nanometer sheet can well be adjusted in stress and the distortion producing in doff lithium process, thereby has weakened greatly the pulverizing problem of particle.The transmission of electronics and lithium ion is also increased dramatically with respect to three dimensional particles in addition.If can produce the micropore running through on two-dimensional nano sheet, more be conducive to storage and the transmission of lithium ion in electrolyte.Therefore by a kind of simple method, prepare porous di-iron trioxide/carbon nanosheet composite material and there is great facilitation for the chemical property of the di-iron trioxide solving.
Summary of the invention
In order to solve above-mentioned technical problem; first object of the present invention is to provide a kind of porous di-iron trioxide/carbon nanosheet composite material and preparation method thereof; this preparation method's technique is simple, is applicable to large-scale production, and has the advantages such as raw material source is abundant, with low cost, safety and environmental protection.Second object of the present invention is to provide lithium ion battery negative material and the lithium ion battery that uses this material.
In order to realize first object of the present invention, the present invention adopts following technical scheme:
A preparation method for porous di-iron trioxide/carbon nanosheet composite material, the method comprises the following steps:
A. take ferrocene and/or ferrocene derivatives and ammonium sulfate as raw material, both are 1:(0.2 ~ 6 according to mass ratio) ratio mix;
B. the mixture after mixing is packed in reactor and sealing;
C. reactor is heated to 400 ℃ ~ 1000 ℃ insulations 0.1 ~ 10 hour;
D. the cooling rear taking-up of question response still sample is wherein heated to 250 ℃ ~ 600 ℃ insulations by the sample of taking-up and within 0.1 ~ 6 hour, can obtains porous di-iron trioxide/carbon nanosheet composite material in air.
As preferably, in described step a, the mass ratio of ferrocene and/or ferrocene derivatives and ammonium sulfate is 1:(0.5 ~ 3); Preferred again, the mass ratio of ferrocene and/or ferrocene derivatives and ammonium sulfate is 1:(1 ~ 2).
As preferably, described ferrocene derivatives is selected one or more mixing in ethyl dicyclopentadienyl iron, ferrocenyl methyl ketone, ferrocenecarboxylic acid
As preferably, in described step b, the mixed media of ferrocene and/or ferrocene derivatives and ammonium sulfate can adopt hand lapping, mechanical ball milling, mechanical agitation or mechanical lapping.
As preferably, in described reactor, atmosphere can be air, nitrogen, argon gas or any two or three gaseous mixture.
As preferably, in described step c, heating-up temperature is 450 ℃ ~ 750 ℃, and temperature retention time is 1 ~ 5 hour; Preferred again, heating-up temperature is 450 ℃ ~ 600 ℃, and temperature retention time is 1 ~ 3 hour.
As preferably, in described steps d, in air, heating-up temperature is 250 ℃ ~ 400 ℃, is incubated 0.2 ~ 3 hour; Preferred again, heating-up temperature is 300 ℃ ~ 400 ℃, and temperature retention time is 1 ~ 2 hour.
The present invention's porous di-iron trioxide/carbon nanosheet composite material that also claimed any one above-mentioned technical scheme obtains.This porous di-iron trioxide/carbon nanosheet composite material has higher specific capacity and excellent cyclical stability as lithium ion battery negative material, after 100 circulations, has the capacity higher than 1000 mAh/g.Have benefited from its unique structure, loose structure is very beneficial for storage and the transmission of lithium ion in electrolyte, and di-iron trioxide nano particle is coated in porous nano carbon plate, greatly improved its electronic conductivity, and effectively can cushion the volume breathing of di-iron trioxide in cyclic process, also greatly reduce the reunion of active material in cyclic process, can effectively improve its chemical property.
In order to realize second object of the present invention, the present invention adopts following technical scheme:
A negative material for lithium ion battery, this negative material is prepared by above-mentioned porous di-iron trioxide/carbon nanosheet composite material.As preferably, this negative material by porous di-iron trioxide/carbon nanosheet composite material, conductive agent and binding agent by 8:(0～2): the quality proportioning of (0.5 ~ 2) joins in solvent and mixes, be coated on collector nickel foam or Copper Foil, then dry, make lithium ion battery negative material.The negative pole that utilization makes, the anodal and preparation of the electrolyte between described negative pole and positive pole and other battery pack that can removal lithium embedded ion become part to prepare lithium ion battery.
In lithium ion battery negative of the present invention, described binding agent can be used conventional binding agent well known by persons skilled in the art, as Kynoar (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC).
In lithium ion battery negative of the present invention, described conductive agent can be used conventional conductive agent well known by persons skilled in the art, as acetylene black, carbon black, gas-phase growth of carbon fibre.
A lithium ion battery, the negative material of this lithium ion battery adopts above-mentioned lithium ion battery negative material.
In lithium ion battery of the present invention, positive electrode that can removal lithium embedded ion can adopt various conventional positive electrode active materials well known by persons skilled in the art, as LiCoO
2, LiFePO
4, LiMnPO
4, LiMnO
2, LiMn
2o
4,, LiFeO
2, LiVPO
4f, LiNiO
2.
In lithium ion battery of the present invention, electrolyte can be conventional nonaqueous electrolytic solution well known by persons skilled in the art, and wherein in electrolyte, lithium salts can be lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), fluorocarbon based Sulfonic Lithium (LiC (SO
2cF
3)
3) in one or more.Nonaqueous solvents can be elected chain acid fat and ring-type acid fat mixed solution as, and wherein chain acid fat can be one or more in dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate fat (EMC); Ring-type acid fat can be one or more in ethylene carbonate (EC), propene carbonate (PC), the sub-ethene fat of carbonic acid (VC).In described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally 0.1 ~ 2 mol/L, and electrolyte used is preferably 0.7 ~ 1.3 mol/L.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention be take ferrocene and/or ferrocene derivatives and ammonium sulfate as raw material; by reactor, heat and air calcination has been synthesized porous di-iron trioxide/carbon nanosheet composite material, this process is simple and easy to control, and product purity is high; abundant raw materials, cost are low, are applicable to large-scale production.
2. di-iron trioxide has the theoretical lithium storage content that is several times as much as commercialization carbon negative pole material as lithium ion battery negative material.Take ferrocene and ammonium sulfate as raw material, and preparation cost is lower.The coating layer of carbon, one side has increased the electronic conductivity of composite material, has improved the utilance of di-iron trioxide, has also improved the dynamic performance of electrode simultaneously; On the other hand, the change in volume that carbon coating layer produces in removal lithium embedded process di-iron trioxide has cushioning effect, has slowed down the efflorescence of ferric oxide particle, has improved its utilance.Porous di-iron trioxide/carbon nanosheet composite material provided by the invention has high specific capacity as lithium ion battery negative material.
3. the density of di-iron trioxide is 5.18 g/cm
3, be density (2.0～2.3 g/cm of material with carbon element
3) 2.5 times, and its theoretical capacity of commercialization carbon negative pole material is 372 mA h/g at present.Thereby the battery of preparing with composite negative pole material of the present invention has the battery of preparing with carbon negative pole material than current business and have more height ratio capacity, volume and capacity ratio and volume energy density are also far above carbon negative pole material.
Accompanying drawing explanation
The stereoscan photograph of porous di-iron trioxide/carbon nanosheet composite material that Fig. 1: embodiment 1 prepares.
The cycle performance of porous di-iron trioxide/carbon nanosheet composite material that Fig. 2: embodiment 1 prepares.
The X ray diffracting spectrum of porous di-iron trioxide/carbon nanosheet composite material that Fig. 3: embodiment 1 prepares.
The stereoscan photograph of porous di-iron trioxide/carbon nanosheet composite material that Fig. 4: embodiment 2 prepares.
The X ray diffracting spectrum of porous di-iron trioxide/carbon nanosheet composite material that Fig. 5: embodiment 2 prepares.
The X ray diffracting spectrum of porous di-iron trioxide/carbon nanosheet composite material that Fig. 6: embodiment 3 prepares.
The capacity voltage curve of porous di-iron trioxide/carbon nanosheet composite material that Fig. 7: embodiment 4 prepares.
The stereoscan photograph of porous di-iron trioxide/carbon nanosheet composite material that Fig. 8: embodiment 5 prepares.
The stereoscan photograph of porous di-iron trioxide/carbon nanosheet composite material that Fig. 9: embodiment 6 prepares.
Embodiment
Following examples can better understand the present invention, but the present invention is also not only confined to following examples.In addition, after having read content of the present invention, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
embodiment 1
After the ferrocene that is 1:1 by mass ratio and ammonium sulfate hand lapping evenly, in being full of the glove box of argon gas, mixture is put into reactor, reactor is heated to 550 ℃ of insulation 3 h.After black product in reactor is taken out, proceed to and in tube furnace, be heated to 350 ℃ and be incubated 1 h and can obtain porous di-iron trioxide/carbon nanosheet composite material.
The preparation of negative pole: the N-methyl-pyrrolidones (NMP) of take is solvent, above-mentioned nanometer sheet is mixed by the quality proportioning of 8:1:1 with conductive agent acetylene black and binding agent Kynoar (PVDF), be coated on collector, then 120 ℃ of oven dry, rolling formation after drying, cut-parts make the negative pole of required size.
The preparation of lithium ion battery: the LiFePO4 that is 8:1:1 by weight ratio, conductive agent acetylene black, polyvinylidene fluoride (PVDF) join in N-methyl-pyrrolidones (NMP) solvent, make anode sizing agent after stirring; It is on the aluminium foil of 1.5 millimeters that anode sizing agent is coated in to thickness equably, rolling formation after drying, and cut-parts make the lithium ion cell positive of 53 millimeters of (length) * 30 millimeter (wide).
After the lithium ion cell positive making, barrier film, negative pole successively lamination is good, include in the square aluminum hull of 55 millimeters * 34 millimeters * 6 millimeters, by the lithium hexafluoro phosphate (LiPF that contains 1 mol/L
6) ethylene carbonate: dimethyl carbonate (EC/DMC) is by volume for 1:1:1 is made into electrolyte, injects electrolytic bath, and sealed cell aluminum hull can make lithium ion battery.
Porous di-iron trioxide/carbon nanosheet composite material capacity and cycle performance test: capacity and the cycle performance of the material that employing simulated battery is prepared the present embodiment are tested.N-methyl-the pyrrolidones (NMP) of take is solvent, preparation-obtained nanometer sheet, acetylene black and binding agent Kynoar (PVDF) are mixed by the quality proportioning of 8:1:1, be coated in collector nickel foam, then after 120 ℃ of oven dry, suppress, make test electrode.Take lithium metal as test electrode is to electrode, adopt 2025 type button cells to test.After test electrode, barrier film (Celgard 2400), lithium sheet metal successively lamination is good, put into 2025 button cell battery cases, with the lithium hexafluoro phosphate (LiPF of 1 mol/L
6) ethylene carbonate: dimethyl carbonate (EC/ DMC, volume ratio is 1:1) solution is as electrolyte, at H
2o and O
2content is all less than in the glove box of 0.1 ppm, utilizes sealing machine sealed cell shell to make lithium ion battery.Adopt Land battery test system to carry out constant current charge-discharge test to assembled simulated battery.Measuring current is 100 mA/g, and voltage range is 0～3V.Adopt this porous di-iron trioxide/carbon nanosheet composite material to there is higher specific capacity and excellent cyclical stability as lithium ion battery negative material, after 100 circulations, there is the capacity higher than 1000 mAh/g.
embodiment 2
After the ferrocene that is 1:1.5 by mass ratio and ammonium sulfate mechanical lapping evenly, in being full of the glove box of nitrogen, mixture is put into reactor, reactor is heated to 550 ℃ of insulation 3h.After black product in reactor is taken out, proceed to and in tube furnace, be heated to 350 ℃ and be incubated 1 h and can obtain porous di-iron trioxide/carbon nanosheet composite material.The material that the present embodiment of take obtains is negative material, adopts the method identical with embodiment 1 to prepare lithium ion battery negative and lithium ion battery.
embodiment 3
After the ferrocene that is 1:0.5 by mass ratio and ammonium sulfate mechanical agitation are even, in being full of the glove box of argon gas, mixture is put into reactor, reactor is heated to 550 ℃ of insulation 1h.After black product in reactor is taken out, proceed to and in tube furnace, be heated to 300 ℃ and be incubated 0.5 h and can obtain porous di-iron trioxide/carbon nanosheet composite material.The composite material that the present embodiment of take obtains is negative material, adopts the method identical with embodiment 1 to prepare lithium ion battery negative and lithium ion battery.
embodiment 4
After the ferrocene that is 1:1 by mass ratio and ammonium sulfate hand lapping evenly, in being full of the glove box of argon gas, mixture is put into reactor, reactor is heated to 650 ℃ of insulation 3h.After black product in reactor is taken out, proceed to and in tube furnace, be heated to 400 ℃ and be incubated 1 h and can obtain porous di-iron trioxide/carbon nanosheet composite material.The composite material that the present embodiment of take obtains is negative material, adopts the method identical with embodiment 1 to prepare lithium ion battery negative and lithium ion battery.
embodiment 5
After the ferrocene that is 1:1.25 by mass ratio and ammonium sulfate hand lapping evenly, in being full of the glove box of argon gas, mixture is put into reactor, reactor is heated to 450 ℃ of insulation 3h.After black product in reactor is taken out, proceed to and in tube furnace, be heated to 250 ℃ and be incubated 1 h and can obtain porous di-iron trioxide/carbon nanosheet composite material.The composite material that the present embodiment of take obtains is negative material, adopts the method identical with embodiment 1 to prepare lithium ion battery negative and lithium ion battery.
embodiment 6
After the ethyl dicyclopentadienyl iron that is 1:1 by mass ratio and ammonium sulfate hand lapping evenly, in being full of the glove box of argon gas, mixture is put into reactor, reactor is heated to 550 ℃ of insulation 3 h.After black product in reactor is taken out, proceed to and in tube furnace, be heated to 350 ℃ and be incubated 1 h and can obtain porous di-iron trioxide/carbon nanosheet composite material.The composite material that the present embodiment of take obtains is negative material, adopts the method identical with embodiment 1 to prepare lithium ion battery negative and lithium ion battery.
Claims (10)
1. a preparation method for porous di-iron trioxide/carbon nanosheet composite material, is characterized in that the method comprises the following steps:
A. take ferrocene and/or ferrocene derivatives and ammonium sulfate as raw material, both are 1:(0.2 ~ 6 according to mass ratio) ratio mix;
B. the mixture after mixing is packed in reactor and sealing;
C. reactor is heated to 400 ℃ ~ 1000 ℃ insulations 0.1 ~ 10 hour;
D. the cooling rear taking-up of question response still sample is wherein heated to 250 ℃ ~ 600 ℃ insulations by the sample of taking-up and within 0.1 ~ 6 hour, can obtains porous di-iron trioxide/carbon nanosheet composite material in air.
2. the preparation method of a kind of porous di-iron trioxide/carbon nanosheet composite material according to claim 1, is characterized in that: in step a, the mass ratio of ferrocene and/or ferrocene derivatives and ammonium sulfate is 1:(0.5 ~ 3); Preferred again, the mass ratio of ferrocene and/or ferrocene derivatives and ammonium sulfate is 1:(1 ~ 2).
3. the preparation method of a kind of porous di-iron trioxide/carbon nanosheet composite material according to claim 1, is characterized in that: ferrocene derivatives is selected one or more mixing in ethyl dicyclopentadienyl iron, ferrocenyl methyl ketone, ferrocenecarboxylic acid.
4. the preparation method of a kind of porous di-iron trioxide/carbon nanosheet composite material according to claim 1, it is characterized in that: in step b, the mixed media of ferrocene and/or ferrocene derivatives and ammonium sulfate can adopt hand lapping, machinery ball milling, mechanical agitation or mechanical lapping; In reactor, atmosphere can be air, nitrogen, argon gas or any two or three gaseous mixture.
5. the preparation method of a kind of porous di-iron trioxide/carbon nanosheet composite material according to claim 1, is characterized in that: in step c, heating-up temperature is 450 ℃ ~ 750 ℃, and temperature retention time is 1 ~ 5 hour; Preferred again, heating-up temperature is 450 ℃ ~ 600 ℃, and temperature retention time is 1 ~ 3 hour.
6. the preparation method of a kind of porous di-iron trioxide/carbon nanosheet composite material according to claim 1, is characterized in that: in steps d, in air, heating-up temperature is 250 ℃ ~ 400 ℃, is incubated 0.2 ~ 3 hour; Preferred again, heating-up temperature is 300 ℃ ~ 400 ℃, and temperature retention time is 1 ~ 2 hour.
7. porous di-iron trioxide/carbon nanosheet composite material that the method described in claim 1 ~ 6 any one claim prepares.
8. a negative material for lithium ion battery, is characterized in that this negative material is prepared by porous di-iron trioxide/carbon nanosheet composite material claimed in claim 7.
9. the negative material of a kind of lithium ion battery according to claim 8, it is characterized in that: this negative material by porous di-iron trioxide/carbon nanosheet composite material, conductive agent and binding agent by 8:(0～2): the quality proportioning of (0.5 ~ 2) joins in solvent and mixes, be coated on collector nickel foam or Copper Foil, then dry, make lithium ion battery negative material.
10. a lithium ion battery, is characterized in that: the negative material of this lithium ion battery adopts the negative material described in claim 8 or 9.
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| CN105762354A (en) * | 2016-05-17 | 2016-07-13 | 安徽师范大学 | Flower-like ferric oxide nanometer material, preparation method thereof, lithium ion battery negative pole and lithium ion battery |
| CN110371924A (en) * | 2019-07-25 | 2019-10-25 | 许昌学院 | A kind of Fe2O3Porous nano line electrode material, preparation method and application |
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