A kind of porous iron sesquioxide/carbon nanosheet composite and preparation method thereof and its application in preparing lithium ion battery
Technical field
The present invention relates to field of lithium ion battery, particularly to a kind of porous iron sesquioxide/carbon nanosheet composite 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 past, Portable mobile electronic device experienced by the development of explosion type, notebook computer, and the various portable type electronic products such as digital camera are widely used, this provides more opportunity to develop for rechargeable secondary cell, it is also proposed more requirement simultaneously. At present, along with the commercialized development of a new generation's electric motor car and hybrid-power electric vehicle, the demand of high-capacity secondary battery increases day by day, in addition the needs of environmental conservation, and people are devoted to tap a new source of energy more and more, to substituting the traditional energy such as coal and oil. In all secondary cells, high power capacity, long circulation life, self discharge be little and the advantage such as high-energy-density, memory-less effect because having for lithium ion battery, obtains tremendous expansion in recent years. As the Typical Representative of a kind of novel energy, lithium ion battery has a fairly obvious advantage, but also has simultaneously and be a lot not enough to be modified, and commercialization electrode material capacity as high in cost, presently used is too low. Negative material used by current commercial Li-ion battery is mainly graphite-like material with carbon element. Owing to graphite-like material with carbon element intrinsic conductivity is high, Stability Analysis of Structures in removal lithium embedded process, there is relatively low embedding de-lithium current potential, and material with carbon element is less expensive, therefore has a clear superiority in commercial applications.But its theoretical capacity low (372mAh/g), it is impossible to 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 circulating and good rate capability is extremely urgent. At present; the new materials such as silicon, stannum, transition metal oxide are counted as the potential substitution material of graphite cathode material; but they there is also obvious defect; as big in the change in volume in embedding de-lithium process; there is relatively low electronic conductivity; thus there is bigger irreversible capacity and stable circulation is poor etc., this also greatly limit scale application of these new materials. Negative material is the important component part of lithium ion battery, and its cycle performance quality directly determines the service life of lithium ion battery. Therefore, seeking 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 widening lithium ion battery has extremely important realistic meaning.
Transition metal oxide, such as Fe2O3、Fe3O4, CuO, CoO etc., the theoretical capacity higher because of it and good safety receive significant attention in recent years. But transition metal oxide can produce bigger change in volume in removal lithium embedded process and cause granule atomization, and oxide mostly is quasiconductor, and therefore electric conductivity is poor, thus greatly reducing its cyclical stability. Currently mainly by material nano and prepare composite etc. transition metal oxide is modified. Material nanoization can be greatly lowered efflorescence and the reunion that granule causes because of embedding de-lithium process, it is possible to is greatly improved the utilization rate of material. By compounds such as the material with carbon elements good with electric conductivity, it is possible to increase the electronic conductivity of metal-oxide, the electrical contact that reinforcing material is overall, additionally the introducing of material with carbon element also can limit the efflorescence of granule significantly.
Fe2O3There is the theoretical capacity of 1007mAh/g as lithium ion battery negative material, it is about 2.7 times of graphite cathode material, in addition it also has the advantages such as with low cost, raw material sources abundant, safety and environmental protection, it it is the lithium ion battery negative material of great prospect, the electronic conductivity relatively low yet with it and cyclic process can produce bigger change in volume and cause granule atomization, therefore its cyclical stability is poor, far below its theoretical capacity. After Chinese invention patent (publication No.: CN102208614A) utilizes iron salt to be hydrolyzed in carbon source solution, calcining prepares the iron sesquioxide negative material that carbon is coated with, and this material has higher capacity and good cyclical stability. Chinese invention patent (publication No.: CN102136565A) is prepared for iron sesquioxide-selenium nano compound film by magnetron sputtering deposition method, and this thin film is used as negative material and has good stability. Above-mentioned patent passes through different experiments method, improves the chemical property of iron sesquioxide, it is shown that iron sesquioxide application prospect in lithium ion battery negative material.
Two-dimensional nano sheet composite is study hotspot in recent years. In lithium ion battery applications, nanometer sheet can well regulate the stress and distortion that produce in embedding de-lithium process, thus reducing the pulverizing problem of granule greatly. Additionally the transmission of electronics and lithium ion is also increased dramatically relative to three dimensional particles. If the micropore run through can be produced on two-dimensional nano sheet, the advantageously storage of lithium ion and transmission in electrolyte. Therefore prepare porous iron sesquioxide/carbon nanosheet composite by a kind of simple method, for the chemical property of iron sesquioxide solved, there is the effect of greatly facilitating.
Summary of the invention
In order to solve above-mentioned technical problem; first purpose of the present invention is to provide a kind of porous iron sesquioxide/carbon nanosheet composite and preparation method thereof; this preparation method technique is simple, is suitable for large-scale production, and has the advantages such as abundant, with low cost, the safety and environmental protection of raw material sources. Second purpose of the present invention is to provide the lithium ion battery negative material and lithium ion battery that use this material.
In order to realize first purpose of the present invention, the present invention adopts following technical scheme:
A kind of preparation method of porous iron sesquioxide/carbon nanosheet composite, the method comprises the following steps:
A. with ferrocene and/or ferrocene derivatives and ammonium sulfate for raw material, both are 1:(0.2 ~ 6 according to mass ratio) ratio mix homogeneously;
B. the mixture after mixing is loaded in reactor and seals;
C. reactor heating is incubated 0.1 ~ 10 hour to 400 DEG C ~ 1000 DEG C;
D. take out wherein sample after the cooling of question response still, the sample of taking-up is heated in atmosphere to 250 DEG C ~ 600 DEG C insulations and porous iron sesquioxide/carbon nanosheet composite within 0.1 ~ 6 hour, can be obtained.
As preferably, in described step a, the mass ratio of ferrocene and/or ferrocene derivatives and ammonium sulfate is 1:(0.5 ~ 3); Further preferably, the mass ratio of ferrocene and/or ferrocene derivatives and ammonium sulfate is 1:(1 ~ 2).
As preferably, described ferrocene derivatives selects 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 or any two or three gaseous mixture.
As preferably, in described step c, heating-up temperature is 450 DEG C ~ 750 DEG C, and temperature retention time is 1 ~ 5 hour; Further preferably, heating-up temperature is 450 DEG C ~ 600 DEG C, and temperature retention time is 1 ~ 3 hour.
As preferably, in described step d, heating-up temperature is 250 DEG C ~ 400 DEG C in atmosphere, is incubated 0.2 ~ 3 hour; Further preferably, heating-up temperature is 300 DEG C ~ 400 DEG C, and temperature retention time is 1 ~ 2 hour.
The present invention is also claimed porous iron sesquioxide/carbon nanosheet composite that any one above-mentioned technical scheme obtains. This porous iron sesquioxide/carbon nanosheet composite has higher specific capacity and excellent cyclical stability as lithium ion battery negative material, has the capacity higher than 1000mAh/g after 100 circulations. Have benefited from the structure of its uniqueness, storage that loose structure is very beneficial in electrolyte lithium ion and transmission, and iron sesquioxide nano-particle is coated in porous nano carbon plate, substantially increase its electronic conductivity, and effectively can cushion iron sesquioxide volume dilational in cyclic process, also the reunion of active substance in cyclic process is greatly reduced, it is possible to be effectively improved its chemical property.
In order to realize second purpose of the present invention, the present invention adopts following technical scheme:
The negative material of a kind of lithium ion battery, this negative material is prepared by above-mentioned porous iron sesquioxide/carbon nanosheet composite. As preferably, this negative material by porous iron sesquioxide/carbon nanosheet composite, conductive agent and binding agent by 8:(0~2): the quality proportioning of (0.5 ~ 2) joins mix homogeneously in solvent, it is coated on collector nickel foam or Copper Foil, then dry, prepare lithium ion battery negative material.Utilize prepare negative pole, can deintercalate lithium ions positive pole and between described negative pole and positive pole electrolyte preparation and other set of cells one-tenth part prepare lithium ion battery.
In the lithium ion battery negative of the present invention, described binding agent can use conventional binders well known by persons skilled in the art, such as Kynoar (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR) and sodium carboxymethyl cellulose (CMC).
In the lithium ion battery negative of the present invention, described conductive agent can use conventional conductive agent well known by persons skilled in the art, such as acetylene black, carbon black, gas-phase growth of carbon fibre.
A kind of lithium ion battery, the negative material of this lithium ion battery adopts above-mentioned lithium ion battery negative material.
In the lithium ion battery of the present invention, it is possible to the positive electrode of deintercalate lithium ions can adopt various conventional cathode active material well known by persons skilled in the art, such as LiCoO2、LiFePO4、LiMnPO4、LiMnO2、LiMn2O4、、LiFeO2、LiVPO4F、LiNiO2。
In the lithium ion battery of the present invention, electrolyte can be common non-aqueous solution liquid well known by persons skilled in the art, and wherein in electrolyte, lithium salts can be lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), fluorocarbon based Sulfonic Lithium (LiC (SO2CF3)3) in one or more. Nonaqueous solvent can elect 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), vinylene carbonate fat (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 method have the advantages that:
1. the present invention is with ferrocene and/or ferrocene derivatives and ammonium sulfate for raw material; being heated by reactor and air calcination has synthesized porous iron sesquioxide/carbon nanosheet composite, this process is simple and easy to control, and product purity is high; abundant raw materials, cost are low, are suitable for large-scale production.
2. iron sesquioxide has the theoretical lithium storage content being several times as much as commercialization carbon negative pole material as lithium ion battery negative material. With ferrocene and ammonium sulfate for raw material, preparation cost is relatively low. The clad of carbon, adds the electronic conductivity of composite on the one hand, improves the utilization rate of iron sesquioxide, also improve the dynamic performance of electrode simultaneously; On the other hand, the change in volume that iron sesquioxide is produced by carbon coating layer in removal lithium embedded process has cushioning effect, slow down the efflorescence of ferric oxide particle, improves its utilization rate. Porous iron sesquioxide/carbon nanosheet composite provided by the invention has high specific capacity as lithium ion battery negative material.
3. the density of iron sesquioxide is 5.18g/cm3, it is the density (2.0~2.3g/cm of material with carbon element3) 2.5 times, and its theoretical capacity of commercialization carbon negative pole material is 372mAh/g at present. Thus the battery prepared with the composite negative pole material of the present invention has the battery prepared than current business carbon negative pole material and has more height ratio capacity, volume and capacity ratio and volume energy density also far above carbon negative pole material.
Accompanying drawing explanation
Fig. 1: the stereoscan photograph of porous iron sesquioxide/carbon nanosheet composite that embodiment 1 prepares.
Fig. 2: the cycle performance of porous iron sesquioxide/carbon nanosheet composite that embodiment 1 prepares.
Fig. 3: the X ray diffracting spectrum of porous iron sesquioxide/carbon nanosheet composite that embodiment 1 prepares.
Fig. 4: the stereoscan photograph of porous iron sesquioxide/carbon nanosheet composite that embodiment 2 prepares.
Fig. 5: the X ray diffracting spectrum of porous iron sesquioxide/carbon nanosheet composite that embodiment 2 prepares.
Fig. 6: the X ray diffracting spectrum of porous iron sesquioxide/carbon nanosheet composite that embodiment 3 prepares.
Fig. 7: the capacity voltage curve of porous iron sesquioxide/carbon nanosheet composite that embodiment 4 prepares.
Fig. 8: the stereoscan photograph of porous iron sesquioxide/carbon nanosheet composite that embodiment 5 prepares.
Fig. 9: the stereoscan photograph of porous iron sesquioxide/carbon nanosheet composite that embodiment 6 prepares.
Detailed description of the invention
Following example can be better understood from the present invention, but the present invention is not limited merely to following example. Additionally, after having read present disclosure, the present invention can be made various changes or modifications by those skilled in the art, these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
By after ferrocene that mass ratio is 1:1 and ammonium sulfate hand lapping uniformly, in the glove box of full argon, mixture is put in reactor, reactor is heated to 550 DEG C of insulation 3h. Proceed to after black product in reactor is taken out and tube furnace heats to 350 DEG C and be incubated 1h and can obtain porous iron sesquioxide/carbon nanosheet composite.
The preparation of negative pole: with N-methyl-pyrrolidon (NMP) for solvent, above-mentioned nanometer sheet is mixed homogeneously by the quality proportioning of 8:1:1 with conductive agent acetylene black and binding agent Kynoar (PVDF), it is coated on collector, then 120 DEG C of drying, rolling formation after drying, cut-parts prepare the negative pole of required size.
The preparation of lithium ion battery: be that the LiFePO4 of 8:1:1, conductive agent acetylene black, polyvinylidene fluoride (PVDF) join in N-methyl-pyrrolidon (NMP) solvent by weight ratio, prepares anode sizing agent after stirring; Being uniformly coated on by anode sizing agent on the aluminium foil that thickness is 1.5 millimeters, rolling formation after drying, cut-parts prepare the lithium ion cell positive of 53 millimeters of (length) × 30 millimeter (width).
Prepared lithium ion cell positive, barrier film, negative pole successively lamination are included in the square aluminum hull of 55 millimeters × 34 millimeters × 6 millimeters after good, by the lithium hexafluoro phosphate (LiPF containing 1 mol/L6) ethylene carbonate: dimethyl carbonate (EC/DMC) is made into electrolyte for 1:1:1 by volume, injects electrolytic bath, and sealed cell aluminum hull can be prepared by lithium ion battery.
Porous iron sesquioxide/carbon nanosheet composite capacity and cycle performance test: capacity and the cycle performance of the material that the present embodiment is prepared by employing simulated battery are tested. With N-methyl-pyrrolidon (NMP) for solvent, by preparation-obtained nanometer sheet, acetylene black and binding agent Kynoar (PVDF) by the quality proportioning mix homogeneously of 8:1:1, it is coated in collector nickel foam, then compacting after 120 DEG C of drying, prepares test electrode. With lithium metal for test counter-electrode, 2025 type button cells are adopted to test. Put in 2025 button cell battery cases after general's test electrode, barrier film (Celgard2400), lithium sheet metal lamination successively are good, with the lithium hexafluoro phosphate (LiPF of 1 mol/L6) ethylene carbonate: solution is as electrolyte for dimethyl carbonate (EC/DMC, volume ratio is 1:1), at H2O and O2Content is respectively less than in the glove box of 0.1ppm, utilizes sealing machine sealed cell shell to prepare lithium ion battery.The Land battery test system simulated battery to assembling is adopted to carry out constant current charge-discharge test. Test electric current is 100mA/g, and voltage range is 0~3V. Adopt this porous iron sesquioxide/carbon nanosheet composite to have higher specific capacity and excellent cyclical stability as lithium ion battery negative material, after 100 circulations, there is the capacity higher than 1000mAh/g.
Embodiment 2
By after ferrocene that mass ratio is 1:1.5 and ammonium sulfate mechanical lapping uniformly, in the glove box of full nitrogen, mixture is put in reactor, reactor is heated to 550 DEG C of insulation 3h. Proceed to after black product in reactor is taken out and tube furnace heats to 350 DEG C and be incubated 1h and can obtain porous iron sesquioxide/carbon nanosheet composite. With the material of the present embodiment acquisition for negative material, the method identical with embodiment 1 is adopted to prepare lithium ion battery negative and lithium ion battery.
Embodiment 3
By ferrocene that mass ratio is 1:0.5 and ammonium sulfate mechanical agitation uniformly after, in the glove box of full argon, mixture is put in reactor, reactor is heated to 550 DEG C of insulation 1h. Proceed to after black product in reactor is taken out and tube furnace heats to 300 DEG C and be incubated 0.5h and can obtain porous iron sesquioxide/carbon nanosheet composite. With the composite of the present embodiment acquisition for negative material, the method identical with embodiment 1 is adopted to prepare lithium ion battery negative and lithium ion battery.
Embodiment 4
By after ferrocene that mass ratio is 1:1 and ammonium sulfate hand lapping uniformly, in the glove box of full argon, mixture is put in reactor, reactor is heated to 650 DEG C of insulation 3h. Proceed to after black product in reactor is taken out and tube furnace heats to 400 DEG C and be incubated 1h and can obtain porous iron sesquioxide/carbon nanosheet composite. With the composite of the present embodiment acquisition for negative material, the method identical with embodiment 1 is adopted to prepare lithium ion battery negative and lithium ion battery.
Embodiment 5
By after ferrocene that mass ratio is 1:1.25 and ammonium sulfate hand lapping uniformly, in the glove box of full argon, mixture is put in reactor, reactor is heated to 450 DEG C of insulation 3h. Proceed to after black product in reactor is taken out and tube furnace heats to 250 DEG C and be incubated 1h and can obtain porous iron sesquioxide/carbon nanosheet composite. With the composite of the present embodiment acquisition for negative material, the method identical with embodiment 1 is adopted to prepare lithium ion battery negative and lithium ion battery.
Embodiment 6
By after ethyl dicyclopentadienyl iron that mass ratio is 1:1 and ammonium sulfate hand lapping uniformly, in the glove box of full argon, mixture is put in reactor, reactor is heated to 550 DEG C of insulation 3h. Proceed to after black product in reactor is taken out and tube furnace heats to 350 DEG C and be incubated 1h and can obtain porous iron sesquioxide/carbon nanosheet composite. With the composite of the present embodiment acquisition for negative material, the method identical with embodiment 1 is adopted to prepare lithium ion battery negative and lithium ion battery.