CN103840132B - Ferrous carbonate/graphene composite material and its preparation method and application - Google Patents
Ferrous carbonate/graphene composite material and its preparation method and application Download PDFInfo
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- CN103840132B CN103840132B CN201410074818.8A CN201410074818A CN103840132B CN 103840132 B CN103840132 B CN 103840132B CN 201410074818 A CN201410074818 A CN 201410074818A CN 103840132 B CN103840132 B CN 103840132B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 76
- 239000004277 Ferrous carbonate Substances 0.000 title claims abstract description 58
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 title claims abstract description 58
- 235000019268 ferrous carbonate Nutrition 0.000 title claims abstract description 58
- 229960004652 ferrous carbonate Drugs 0.000 title claims abstract description 58
- 229910000015 iron(II) carbonate Inorganic materials 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 208000011580 syndromic disease Diseases 0.000 claims abstract description 8
- 229910001868 water Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000006229 carbon black Substances 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000011790 ferrous sulphate Substances 0.000 description 10
- 235000003891 ferrous sulphate Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- -1 and conductive black Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZWOYKDSPPQPUTC-UHFFFAOYSA-N dimethyl carbonate;1,3-dioxolan-2-one Chemical compound COC(=O)OC.O=C1OCCO1 ZWOYKDSPPQPUTC-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 present invention relates to technical field of inorganic material, disclose the preparation method of a kind of ferrous carbonate/graphene composite material for lithium ion battery negative material, it includes, step one: with water, grapheme material, water-soluble ferrous salt, urea are formed suspension；Wherein, described grapheme material is 0.02～0.2: 1 with the mass ratio of described water-soluble ferrous salt；Described urea is 20～100: 1 with the ratio of the substance withdrawl syndrome of described water-soluble ferrous salt；Step 2: insert in reactor by described suspension, control temperature is 100～180 DEG C and carries out hydro-thermal reaction 4～12h, it is thus achieved that ferrous carbonate/graphene composite material.It is lithium ion battery prepared by negative material that the present invention also provides for this ferrous carbonate/graphene composite material.The present invention uses low-temperature hydrothermal carbonate synthesis ferrous iron/Graphene negative material, and specific capacity is high, cyclicity is good, is applied to lithium ion battery negative material and has good development prospect.
Description
Technical field
The invention belongs to inorganic new energy materials field, particularly relate to preparation and the application of the Novel anode material of a kind of lithium ion battery.
Background technology
Due to needed for new-energy automobile high-power power battery in the urgent need to, and lithium-ion-power cell presently, there are the bottleneck problem such as price and security, and lithium-ion-power cell critical material is faced with new challenge.Lithium ion battery negative material is based on graphitized carbon material at present, but the SEI film that material with carbon element generates in discharge process first, irreversible capacity loss can be caused, sometimes also result in change and the poor electric contact of carbon electrode internal structure；Battery failure may be caused because of the decomposition of protective layer or causes safety issue during high temperature；The unit volume capacity of graphite cathode is relatively low simultaneously, it is difficult to meet the requirement of the field high energy density cells such as such as electric automobile, wind and solar energy energy storage, intelligent grid energy storage and conversion.Therefore, the negative material of research and development high power capacity and high performance-price ratio is very urgent.
" transformant " negative material ferrous carbonate is as novel lithium ion battery negative material, and compared with the graphite cathode of current commercialization, it has higher theoretical capacity, wide applicability, good stability etc. advantage.Meanwhile, when in Lithium-ion embeding to ferrous carbonate, the Li obtained by reaction2CO3The Li reacting gained in traditional metal oxide it is embedded into than it2O is stable so that ferrous carbonate can keep the lasting discharge and recharge of high current density.
But, owing to active material relates to substantial amounts of structural rearrangement and Volume Changes in charge and discharge process, this phenomenon can cause the separation of its particle and rupture, thus causes the decay of capacity.These problems that Volume Changes in charge and discharge process causes not only occur in alloy-type electrode, the most often occur in conversion hysteria electrode.Therefore, in order to improve electric conductivity and the stability of electrode material, people are devoted to active material and other material are carried out composite modified research.
Such as, Graphene, as the material with carbon element of two dimension, has high specific surface area, electrical conductivity and the advantage such as thermal conductivity, flexibility.The specific surface area that Graphene is high is conducive to it can fully obtain the infiltration of electrolyte, thus lithium ion can sufficiently be spread.High electrical conductivity can make it greatly shorten the discharge and recharge time, and high thermal conductivity enables to the security of battery and well ensured.Simultaneously as surface of graphene oxide contains substantial amounts of oxygen-containing functional group, when with other materials compound tense, it is possible to make other materials be uniformly distributed in its surface, improve dispersiveness.
Additionally, hydro-thermal method is in special closed reactor (autoclave), by reaction system (the generally aqueous solution) is carried out particular procedure, produce relatively-high temperature, a reaction environment for high pressure, usual indissoluble, material insoluble in popular response system can be dissolved and recrystallize in this reaction system, thus carry out the synthesis of inorganic material and a kind of method of process.Compared with other powder preparing methods, hydro-thermal method has following advantages: the particle of powder is tiny and uniform, and grain development is complete, and be easy to get suitable stoichiometric proportion and grain form；Reaction process condition is simple, it is not necessary to use mechanical milling process.
So, it is intended that hydro-thermal method can be utilized to obtain a kind of novel composite be applied to field of batteries.
Summary of the invention
It is an object of the invention to for metal and the cyclical stability of metal oxide negative material thereof and high rate performance not enough, it is provided that a kind of specific capacity is high, the new negative electrode materials for lithium secondary batteries ferrous carbonate/graphene composite material of good cycling stability and its preparation method and application.
The preparation method of this ferrous carbonate/graphene composite material, comprises the steps:
Step one: grapheme material, water-soluble ferrous salt, urea are configured to suspension with water；Wherein, described grapheme material is 0.02～0.2: 1 with the mass ratio of described water-soluble ferrous salt；Described urea is 20～100: 1 with the ratio of the substance withdrawl syndrome of described water-soluble ferrous salt；
Step 2: insert in reactor by described suspension, controlling temperature is 100～180 DEG C of reactions 4～12h, it is thus achieved that ferrous carbonate/graphene composite material.
Further, described step one is first to be added to the dispersion liquid of Graphene and water by described water-soluble ferrous salt, it is thus achieved that dispersion liquid, then adds urea mixing toward described dispersion liquid and is configured to suspension.
Further, described grapheme material is graphene oxide.
Further, the substance withdrawl syndrome of described water-soluble ferrous salt is 0.02～0.05mol/L.
Further, described water-soluble ferrous salt is ferrous sulfate, water soluble halogenated ferrous salt.
The present invention also provides for a kind of ferrous carbonate/graphene composite material, and described ferrous carbonate is 1.375: 1～14.4: 1 with the mass ratio of Graphene.
Further, described grapheme material is graphene oxide.
The present invention also provides for the lithium ion battery utilizing above-mentioned a kind of ferrous carbonate/graphene composite material to prepare.Lithium ion battery includes positive pole and negative pole, the material of described negative pole includes: ferrous carbonate/graphene composite material, and conductive black, binding agent, wherein, described ferrous carbonate/graphene composite material, conductive black, the mass ratio of binding agent are 7～8: 1～2: 1.
Further, described binding agent is Vingon.
Compared with prior art, there is advantages that
1, ferrous carbonate prepared by the present invention/graphene composite material specific capacity height, good cycle, be applied to lithium ion battery negative material and have good application development prospect.
2, lithium ion battery negative material carbon acid ferrous iron/grapheme material that the present invention prepares with hydro-thermal method is as nano-scale.The big specific surface area of Graphene and small size, one contributes to the infiltration of electrolyte, and two can reduce lithium ion diffusion length in ferrous carbonate, is conducive to improving the storage lithium specific capacity of ferrous carbonate；Grapheme material has good electric conductivity simultaneously, thus improves its chemical property.
3, the present invention uses low-temperature hydrothermal synthetic technology, and process conditions are easy to control, and synthetic method is simple, workable, reproducible.
4, the present invention uses Graphene, ferrous salt and urea to be raw material, wide material sources, low cost.
Accompanying drawing explanation
Fig. 1 is the x-ray diffractogram of powder of ferrous carbonate/graphene composite material in the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture of ferrous carbonate/graphene composite material in the embodiment of the present invention 1.
Fig. 3 is lithium ion battery that in the embodiment of the present invention 1 prepared by the ferrous carbonate/graphene composite material initial charge (curve 1) under 0.05～3.0V, 200mA/g current density, electric discharge (curve 2) curve map.
Fig. 4 is lithium ion battery that in the embodiment of the present invention 1 prepared by the ferrous carbonate/graphene composite material cycle performance curve map under 0.05～3.0V, 200mA/g current density.
Fig. 5 is the transmission electron microscope picture of ferrous carbonate/graphene composite material in the embodiment of the present invention 2.
Fig. 6 is lithium ion battery that in the embodiment of the present invention 2 prepared by the ferrous carbonate/graphene composite material cycle performance curve map under 0.05～3.0V, 200mA/g current density.
Fig. 7 is the transmission electron microscope picture of ferrous carbonate/graphene composite material in the embodiment of the present invention 3.
Fig. 8 is lithium ion battery that in the embodiment of the present invention 3 prepared by the ferrous carbonate/graphene composite material cycle performance curve map under 0.05～3.0V, 200mA/g current density.
Detailed description of the invention
The present invention is further illustrated below in conjunction with the accompanying drawings with specific embodiment.Test method used in following embodiment if no special instructions, is conventional method；The material that used, reagent etc., if no special instructions, for the reagent commercially obtained and material.
Instrument used by scanning electron microscope analysis described in each embodiment is the pattern that TECNAI12 type transmission electron microscope (TEM) of Holland FEI observes sample, voltage is 20～120KV, sample preparation drips on copper mesh after using absolute ethyl alcohol dispersion, air drying.
Instrument used by X-ray diffraction analysis is the crystal phase structure that Beijing Pu Xi all purpose instrument Co., Ltd XD-2 type X-ray diffractometer (XRD) characterizes prepared end product.Test condition is Cu target, K α radiation, 36kV, 30mA, step width 0.02 °, sweep limits 15～80 °.Sample is that powder is placed in the pressing of sample stage groove, directly detects.
Instrument used by charge-discharge test is the BTS51800 battery test system of new Weir Electronics Co., Ltd. of Shenzhen, and model is CT-3008W, carries out 200mA/g current density charge-discharge test in 0.05～3.0V voltage range.
Embodiment 1
Step one: weigh in the beaker that 0.020g graphene oxide is equipped with 40mL deionized water, mixing, then it is configured to graphene oxide dispersion A through ultrasonic disperse.Then green vitriol is added to described dispersion liquid A, stirring and dissolving, it is thus achieved that the dispersion liquid B of ferrous sulfate, Graphene and water.Wherein graphene oxide is 0.09: 1 with the mass ratio of ferrous sulfate.
It is 30: 1 by the substance withdrawl syndrome ratio of urea with ferrous sulfate again, in described dispersion liquid B, adds urea, after stirring makes urea be completely dissolved, obtain suspension C.
Step 2: shift described suspension C in teflon-lined stainless steel cauldron, is placed in convection oven at 120 DEG C reaction 8 hours.The product deionized water obtained and ethanol cyclic washing, i.e. obtain ferrous carbonate/graphene composite material.Fig. 1 shows the XRD of the powder of ferrous carbonate/graphene composite material it was confirmed there is ferrous carbonate in obtained composite.Fig. 2 shows that TEM figure (2900 times) of this ferrous carbonate/graphene composite material, the most visible ferrous carbonate nanometer rods cover in surface of graphene oxide.
Mass Calculation according to the composite obtained may know that, in composite, ferrous carbonate is 2.85: 1 with the mass ratio of Graphene.
Below ferrous carbonate/the graphene composite material obtained in embodiment is prepared as lithium ion battery.
Ferrous carbonate/the graphene composite material obtained in embodiment is mixed with conductive carbon black, binding agent Vingon (PVDF) in mass ratio 8: 1: 1, adding appropriate 1-METHYLPYRROLIDONE (NMP) makes above-mentioned three kinds of materials stir as solvent, it is applied on Copper Foil, vacuum drying oven is dried at 90 DEG C, treat that solvent volatilization is clean, obtain ferrous carbonate/graphene composite material electrode slice at sheet-punching machine top shear blade.Gained ferrous carbonate/graphene composite material electrode slice is done negative pole, metal lithium sheet is positive pole, electrolyte is for containing ethylene carbonate-dimethyl carbonate mixed system (can be called for short EC+DMC mixed system) that 1MLiPF6, volume ratio are 1: 1, barrier film is microporous polypropylene membrane (Celgard2400), is assembled into CR2025 type fastening lithium ionic cell in the glove box of full argon gas (Ar).
Lithium ion battery to above-mentioned acquisition carries out electrochemical property test below, uses new Weir Electronics Co., Ltd. of Shenzhen BTS51800 battery test system to carry out charge-discharge performance test.
Can be seen that from Fig. 3 and Fig. 4 this material 0.05～3.0V, the first discharge specific capacity under 200mA/g current density reaches 1505mAh/g, and maintains 751mAh/g through 100 circulation specific discharge capacities.Visible, ferrous carbonate/graphene composite material has preferable chemical property, uses its lithium ion battery made to have and more preferably circulates discharge performance.
Embodiment 2
Step one: weigh 0.040g graphene oxide and be equipped with the mixing of 40mL deionized water, be configured to graphene oxide dispersion A through ultrasonic disperse.Then green vitriol is added to described dispersion liquid A, stirring and dissolving, it is thus achieved that the dispersion liquid B of ferrous sulfate, Graphene and water.Wherein graphene oxide is 0.18: 1 with the mass ratio of ferrous sulfate.
It is 100: 1 by the substance withdrawl syndrome ratio of urea with ferrous sulfate again, in described dispersion liquid B, adds urea, after stirring makes urea be completely dissolved, obtain suspension C.
Step 2: shift described suspension C in teflon-lined stainless steel cauldron, is then placed in convection oven at 180 DEG C reaction 12 hours by reactor.The product deionized water obtained and ethanol cyclic washing, i.e. obtain ferrous carbonate/graphene composite material, and wherein ferrous carbonate is 1.375: 1 with the mass ratio of Graphene.Fig. 5 shows TEM figure (18500 times) of this ferrous carbonate/graphene composite material, it is seen that ferrous carbonate nanometer rods covers in surface of graphene oxide.
According to the method for embodiment 1, the ferrous carbonate/graphene composite material obtained in the present embodiment is prepared as lithium ion battery.New Weir Electronics Co., Ltd. of Shenzhen BTS51800 battery test system is used to carry out charge-discharge performance test.As shown in Figure 6, as can be seen from Figure 6 this material is 0.05～3.0V for cycle performance curve map, and the first discharge specific capacity under 200mA/g current density reaches 1682mAh/g, and maintains 392mAh/g through 80 circulation specific discharge capacities.
Embodiment 3
Step one: weigh 0.005g graphene oxide and add the mixing of 40mL deionized water, be configured to graphene oxide dispersion A through ultrasonic disperse.Then green vitriol is added to described dispersion liquid A, stirring and dissolving, it is thus achieved that the dispersion liquid B of ferrous sulfate, Graphene and water.Wherein graphene oxide is 0.02: 1 with the mass ratio of ferrous sulfate.
It is 20: 1 by the substance withdrawl syndrome ratio of urea with ferrous sulfate again, in described dispersion liquid B, adds urea, after stirring makes urea be completely dissolved, obtain suspension C.
Step 2: shift described suspension C in teflon-lined stainless steel cauldron, is then placed in convection oven at 100 DEG C reaction 4 hours by reactor.The product deionized water obtained and ethanol cyclic washing, i.e. obtain ferrous carbonate/graphene composite material, and wherein ferrous carbonate is 14.4: 1 with the mass ratio of Graphene.
Fig. 7 shows the TEM figure of this ferrous carbonate/graphene composite material, it is seen that the little bar-shaped solid that in figure, color is deeper is ferrous carbonate nanometer rods, and ferrous carbonate nanometer rods completely covers graphene film.
According to the method for embodiment 1, the ferrous carbonate/graphene composite material obtained in the present embodiment is prepared as lithium ion battery.New Weir Electronics Co., Ltd. of Shenzhen BTS51800 battery test system is used to carry out charge-discharge performance test.As shown in Figure 8, as can be seen from Figure 8 this material is 0.05～3.0V, and the first discharge specific capacity under 200mA/g current density reaches 1417mAh/g for cycle performance curve map, maintains 875mAh/g through 80 circulation specific discharge capacities.Visible ferrous carbonate/graphene composite material has good chemical property, uses its lithium ion battery made to have more preferably stable circulation performance.
Claims (5)
1. the preparation method of ferrous carbonate/graphene composite material, it is characterised in that
Comprise the steps:
Step one: water solubility ferrous salt is added to graphene dispersing solution, it is thus achieved that dispersion liquid,
Then add urea mixing toward described dispersion liquid and be configured to suspension；Wherein, described urea and institute
The ratio of the substance withdrawl syndrome stating water-soluble ferrous salt is 20～100: 1；
Wherein, described grapheme material is graphene oxide, and described water-soluble ferrous salt is sulfuric acid
Ferrous iron, the substance withdrawl syndrome of described water-soluble ferrous salt is 0.02～0.05mol/L；
Step 2: insert in reactor by described suspension, controlling temperature is 100～180 DEG C
Carry out hydro-thermal reaction 4～12h, it is thus achieved that ferrous carbonate/graphene composite material, described carbonic acid
Ferrous and Graphene mass ratio is 1.375～14.4: 1.
2. ferrous carbonate/graphene composite material, it is characterised in that for claim 1
Described preparation method prepare, in described ferrous carbonate/graphene composite material ferrous carbonate with
The mass ratio of Graphene is 1.375～14.4: 1.
The most according to claim 2, ferrous carbonate/graphene composite material, its feature exists
In, described grapheme material is graphene oxide.
4. a lithium ion battery, it includes positive pole and negative pole, it is characterised in that described negative
The material of pole includes: the ferrous carbonate/graphene composite material described in Claims 2 or 3,
And conductive black, binding agent, wherein, described ferrous carbonate/graphene composite material, lead
Electricity carbon black, the mass ratio of binding agent are 7～8: 1～2: 1.
Lithium ion battery the most according to claim 4, it is characterised in that described binding agent
For Vingon.
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| CN108336304B (en) * | 2017-12-27 | 2020-09-11 | 洛阳理工学院 | Hydrothermal method for preparing stainless steel mesh loaded FeCO3Method for preparing negative plate |
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