CN103840132A - Ferrous carbonate/graphene composite material and preparation method and applications thereof - Google Patents
Ferrous carbonate/graphene composite material and preparation method and applications thereof Download PDFInfo
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- CN103840132A CN103840132A CN201410074818.8A CN201410074818A CN103840132A CN 103840132 A CN103840132 A CN 103840132A CN 201410074818 A CN201410074818 A CN 201410074818A CN 103840132 A CN103840132 A CN 103840132A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 80
- 239000004277 Ferrous carbonate Substances 0.000 title claims abstract description 62
- 229960004652 ferrous carbonate Drugs 0.000 title claims abstract description 62
- 229910000015 iron(II) carbonate Inorganic materials 0.000 title claims abstract description 62
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 title claims abstract description 61
- 235000019268 ferrous carbonate Nutrition 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 11
- 239000011790 ferrous sulphate Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 7
- -1 ferrous halide salt Chemical class 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000007773 negative electrode material Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 229910000859 α-Fe Inorganic materials 0.000 abstract 3
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 230000008569 process Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 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
- 238000001132 ultrasonic dispersion Methods 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
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal 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
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- 208000032953 Device battery issue Diseases 0.000 description 1
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- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- ZWOYKDSPPQPUTC-UHFFFAOYSA-N dimethyl carbonate;1,3-dioxolan-2-one Chemical compound COC(=O)OC.O=C1OCCO1 ZWOYKDSPPQPUTC-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 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
- 239000000203 mixture Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing 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
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- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
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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
- H01M4/62—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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- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 invention relates to the technical field of inorganic materials, and discloses a preparation method for a ferrous carbonate/graphene composite material. The preparation method comprises the steps of: I. mixing graphene materials, water-soluble ferrite, urea and water to form a suspension, wherein the mass ratio of the graphene materials to the water-soluble ferrite is (0.02-0.2):1, and the amount-of-substance concentration ratio of the urea to the water-soluble ferrite is (20-100):1; II. putting the suspension into a reaction kettle, controlling the temperature to be 100-180DEG C, and carrying out hydrothermal reaction for 4-12h to obtain the ferrous carbonate/graphene composite material. The invention further provides a lithium ion battery prepared by taking the ferrous carbonate/graphene composite material as a negative electrode material. By being synthesized through low-temperature hydrothermal reaction, the ferrous carbonate/graphene composite material is high in specific capacity and good in cycling performance, and has excellent development prospects after being applied to the negative electrode materials of the lithium ion battery.
Description
Technical field
The invention belongs to inorganic new energy materials field, relate in particular to a kind of preparation and application of Novel anode material of lithium ion battery.
Background technology
Due to the required high-power power battery of new-energy automobile in the urgent need to, and there is the bottleneck problem such as price and fail safe in lithium-ion-power cell at present, lithium-ion-power cell critical material is being faced with new challenge.At present lithium ion battery negative material is take graphitized carbon material as main, but the SEI film that material with carbon element generates in discharge process first can cause irreversible capacity loss, sometimes also can cause variation and the poor electric contact of carbon electrode internal structure; May be because of the decomposition of protective layer when high temperature, cause battery failure or cause safety issue; The unit volume capacity relative of graphite cathode is lower simultaneously, is difficult to meet requirement field high energy density cells 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 current commercial graphite cathode, it has higher theoretical capacity, applicability widely, good stability etc. advantage.Meanwhile, in the time that lithium ion is embedded in ferrous carbonate, the Li that reaction obtains
2cO
3be embedded into than it Li that reacts gained in traditional metal oxide
2o is stable, make ferrous carbonate can keep high current density continue discharge and recharge.
But because active material relates to a large amount of structural rearrangements and change in volume in charge and discharge process, this phenomenon can cause the separation of its particle and break, thereby cause the decay of capacity.These problems that change in volume in charge and discharge process causes not only appear in alloy-type electrode, in conversion hysteria electrode, also often occur.Therefore,, in order to improve conductivity and the stability of electrode material, people are devoted to active material and other material to carry out composite modified research.
For example, Graphene, as two-dimentional material with carbon element, has the advantages such as high specific area, conductivity and thermal conductivity, flexibility.The specific area that Graphene is high is conducive to it and can fully obtains the infiltration of electrolyte, thereby lithium ion can be spread fully.High conductivity can make it shorten widely the time of discharging and recharging, and high thermal conductivity can make the fail safe of battery well be ensured.Meanwhile, because a large amount of oxygen-containing functional groups is contained on graphene oxide surface, when with other materials compound tense, can make other materials be uniformly distributed in its surface, improve dispersed.
In addition, hydro thermal method is in special closed reactor (autoclave), by reaction system (being generally the aqueous solution) is carried out to particular procedure, produce the reaction environment of a relatively-high temperature, high pressure, the material that make usual indissoluble, is insoluble to popular response system can dissolve and recrystallization in this reaction system, thus a kind of method of carrying out the synthetic of inorganic material and processing.Compare with other powder preparing methods, hydro thermal method has following advantages: the particle of powder is tiny and even, and crystal grain is grown complete, and suitable stoichiometric proportion and grain form are easy to get; Reaction process condition is simple, does not need to use mechanical milling process.
So people expect to utilize a kind of novel composite material of hydro thermal method acquisition to be applied to field of batteries.
Summary of the invention
The object of the invention is cyclical stability and high rate performance deficiency for metal and metal oxide negative material thereof, provide that a kind of specific capacity is high, the new negative electrode materials for lithium secondary batteries of good cycling stability---ferrous carbonate/graphene composite material and its preparation method and application.
The preparation method of this ferrous carbonate/graphene composite material, comprises the steps:
Step 1: grapheme material, water-soluble ferrous salt, urea and water are mixed with to suspension; Wherein, the mass ratio of described grapheme material and described water-soluble ferrous salt is 0.02～0.2: 1; Described urea is 20～100: 1 with the ratio of the amount of substance concentration of described water-soluble ferrous salt;
Step 2: described suspension is inserted in reactor, and controlling temperature is 100～180 ℃ of reaction 4～12h, obtains ferrous carbonate/graphene composite material.
Further, described step 1 is first described water-soluble ferrous salt to be added in the dispersion liquid of Graphene and water, obtains dispersion liquid, then adds urea to mix toward described dispersion liquid and is mixed with suspension.
Further, described grapheme material is graphene oxide.
Further, the amount of substance concentration of described water-soluble ferrous salt is 0.02～0.05mol/L.
Further, described water-soluble ferrous salt is ferrous sulfate, water-soluble ferrous halide salt.
The present invention also provides a kind of ferrous carbonate/graphene composite material, and the mass ratio of described ferrous carbonate and Graphene is 1.375: 1～14.4: 1.
Further, described grapheme material is graphene oxide.
The present invention also provides the lithium ion battery that utilizes above-mentioned a kind of ferrous carbonate/graphene composite material to prepare.Lithium ion battery comprises positive pole and negative pole, the material of described negative pole comprises: ferrous carbonate/graphene composite material, and conductive black, binding agent, wherein, the mass ratio of described ferrous carbonate/graphene composite material, conductive black, binding agent is 7～8: 1～2: 1.
Further, described binding agent is Vingon.
Compared with prior art, the present invention has following beneficial effect:
1, the ferrous carbonate/graphene composite material specific capacity that prepared by the present invention is high, good cycle, is applied to lithium ion battery negative material and has good application development prospect.
2, lithium ion battery negative material carbon acid ferrous iron/grapheme material that the present invention prepares take hydro thermal method is nano-scale.Large specific area and the small size of Graphene, one contributes to the infiltration of electrolyte, and two can reduce the diffusion length of lithium ion in ferrous carbonate, are conducive to improve the storage lithium specific capacity of ferrous carbonate; Grapheme material has good conductivity simultaneously, thereby improves its chemical property.
3, the present invention adopts low-temperature hydrothermal synthetic technology, and process conditions are easy to control, and synthetic method is simple, workable, reproducible.
4, to adopt Graphene, ferrous salt and urea be raw material in the present invention, wide material sources, and cost is low.
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 ferrous carbonate/graphene composite material initial charge (curve 1), electric discharge (curve 2) curve chart under 0.05～3.0V, 200mA/g current density.
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 chart 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 chart 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 chart under 0.05～3.0V, 200mA/g current density.
Embodiment
Further illustrate the present invention below in conjunction with the drawings and specific embodiments.The test method using in following embodiment if no special instructions, is conventional method; The material, the reagent etc. that use if no special instructions, are reagent and the material that can obtain from commercial channels.
The TECNAI12 type transmission electron microscope (TEM) that the instrument used of scanning electron microscope analysis described in each embodiment is Dutch FEI is observed the pattern of sample, voltage is 20～120KV, sample preparation drips on copper mesh after adopting absolute ethyl alcohol to disperse, air drying.
X-ray diffraction analysis instrument used is the crystal phase structure that Beijing XD-2 of Pu Xi all purpose instrument Co., Ltd type X-ray diffractometer (XRD) characterizes prepared end product.Test condition is Cu target, K α radiation, 36kV, 30mA, walk wide 0.02 °, 15～80 ° of sweep limitss.Sample is that powder is placed in the pressing of sample stage groove, direct-detection.
Charge-discharge test instrument used 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.
Step 1: take 0.020g graphene oxide and add in the beaker that 40mL deionized water is housed, mix, then be mixed with graphene oxide dispersion liquid A through ultrasonic dispersion.Then green vitriol is added in described dispersion liquid A to stirring and dissolving, the dispersion liquid B of acquisition ferrous sulfate, Graphene and water.Wherein the mass ratio of graphene oxide and ferrous sulfate is 0.09: 1.
Be 30: 1 by the amount of substance concentration ratio of urea and ferrous sulfate again, in described dispersion liquid B, add urea, after stirring is dissolved urea completely, obtain suspension C.
Step 2: shift described suspension C in teflon-lined stainless steel cauldron, be placed in convection oven and react at 120 ℃ 8 hours.Deionized water and ethanol cyclic washing for the product obtaining, obtain ferrous carbonate/graphene composite material.Fig. 1 shows the XRD figure of the powder of ferrous carbonate/graphene composite material, has confirmed to have ferrous carbonate in acquisition composite material.Fig. 2 shows the TEM figure (2900 times) of this ferrous carbonate/graphene composite material, and further visible ferrous carbonate nanometer rods covers graphene oxide surface.
Can know according to the Mass Calculation of obtained composite material, in composite material, the mass ratio of ferrous carbonate and Graphene is 2.85: 1.
Ferrous carbonate/the graphene composite material obtaining in embodiment is prepared as to lithium ion battery below.
Ferrous carbonate/the graphene composite material obtaining in embodiment is mixed in mass ratio with conductive carbon black, binding agent Vingon (PVDF) at 8: 1: 1, add again appropriate 1-METHYLPYRROLIDONE (NMP) as solvent, above-mentioned three kinds of materials to be stirred, be applied on Copper Foil, in vacuum drying oven, at 90 ℃, dry, treat that solvent evaporates 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 to negative pole, metal lithium sheet is anodal, 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 that is full of argon gas (Ar).
The lithium ion battery of above-mentioned acquisition is carried out to electrochemical property test below, adopt the new Weir BTS51800 of Electronics Co., Ltd. of Shenzhen battery test system to carry out charge-discharge performance test.
From Fig. 3 and Fig. 4, can find out that this material is at 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 good chemical property, adopts the lithium ion battery of its making to have better circulation discharge performance.
Step 1: take 0.040g graphene oxide and add and 40mL deionized water is housed mixes, be mixed with graphene oxide dispersion liquid A through ultrasonic dispersion.Then green vitriol is added in described dispersion liquid A to stirring and dissolving, the dispersion liquid B of acquisition ferrous sulfate, Graphene and water.Wherein the mass ratio of graphene oxide and ferrous sulfate is 0.18: 1.
Be 100: 1 by the amount of substance concentration ratio of urea and ferrous sulfate again, in described dispersion liquid B, add urea, after stirring is dissolved urea completely, obtain suspension C.
Step 2: shift described suspension C in teflon-lined stainless steel cauldron, then reactor is placed in to convection oven and reacts at 180 ℃ 12 hours.Deionized water and ethanol cyclic washing for the product obtaining, obtain ferrous carbonate/graphene composite material, and wherein the mass ratio of ferrous carbonate and Graphene is 1.375: 1.Fig. 5 shows the TEM figure (18500 times) of this ferrous carbonate/graphene composite material, and visible ferrous carbonate nanometer rods covers graphene oxide surface.
According to the method for embodiment 1, the ferrous carbonate/graphene composite material obtaining in the present embodiment is prepared as to lithium ion battery.Adopt the new Weir BTS51800 of Electronics Co., Ltd. of Shenzhen battery test system to carry out charge-discharge performance test.As shown in Figure 6, as can be seen from Figure 6 this material is at 0.05～3.0V for cycle performance curve chart, 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 1: take 0.005g graphene oxide and add 40mL deionized water to mix, be mixed with graphene oxide dispersion liquid A through ultrasonic dispersion.Then green vitriol is added in described dispersion liquid A to stirring and dissolving, the dispersion liquid B of acquisition ferrous sulfate, Graphene and water.Wherein the mass ratio of graphene oxide and ferrous sulfate is 0.02: 1.
Be 20: 1 by the amount of substance concentration ratio of urea and ferrous sulfate again, in described dispersion liquid B, add urea, after stirring is dissolved urea completely, obtain suspension C.
Step 2: shift described suspension C in teflon-lined stainless steel cauldron, then reactor is placed in to convection oven and reacts at 100 ℃ 4 hours.Deionized water and ethanol cyclic washing for the product obtaining, obtain ferrous carbonate/graphene composite material, and wherein the mass ratio of ferrous carbonate and Graphene is 14.4: 1.
Fig. 7 shows the TEM figure of this ferrous carbonate/graphene composite material, and in visible figure, the darker little bar-shaped solid of color is ferrous carbonate nanometer rods, and ferrous carbonate nanometer rods has covered graphene film completely.
According to the method for embodiment 1, the ferrous carbonate/graphene composite material obtaining in the present embodiment is prepared as to lithium ion battery.Adopt the new Weir BTS51800 of Electronics Co., Ltd. of Shenzhen battery test system to carry out charge-discharge performance test.As shown in Figure 8, as can be seen from Figure 8 this material is at 0.05～3.0V for cycle performance curve chart, and the first discharge specific capacity under 200mA/g current density reaches 1417mAh/g, maintains 875mAh/g through 80 circulation specific discharge capacities.Visible ferrous carbonate/graphene composite material has good chemical property, adopts the lithium ion battery of its making to have better stable circulation performance.
Claims (9)
1. a preparation method for ferrous carbonate/graphene composite material, is characterized in that, comprises the steps:
Step 1: grapheme material, water-soluble ferrous salt, urea and water are mixed with to suspension; Wherein, the mass ratio of described grapheme material and described water-soluble ferrous salt is 0.02～0.2: 1; Described urea is 20～100: 1 with the ratio of the amount of substance concentration of described water-soluble ferrous salt;
Step 2: described suspension is inserted in reactor, and control temperature is 100～180 ℃ and carries out hydro-thermal reaction 4～12h, obtains ferrous carbonate/graphene composite material.
2. the preparation method of ferrous carbonate/graphene composite material according to claim 1, it is characterized in that, described step 1 is first described water-soluble ferrous salt to be added in graphene dispersing solution, obtains dispersion liquid, then adds urea to mix toward described dispersion liquid and is mixed with suspension.
3. the preparation method of ferrous carbonate/graphene composite material according to claim 1, is characterized in that, described grapheme material is graphene oxide.
4. the preparation method of ferrous carbonate/graphene composite material according to claim 1, is characterized in that, the amount of substance concentration of described water-soluble ferrous salt is 0.02～0.05mol/L.
5. according to the preparation method of ferrous carbonate/graphene composite material described in claim 1 or 4, it is characterized in that, described water-soluble ferrous salt is ferrous sulfate, water-soluble ferrous halide salt.
6. ferrous carbonate/graphene composite material, is characterized in that, the mass ratio of described ferrous carbonate and Graphene is 1.375～14.4: 1.
7. ferrous carbonate/graphene composite material according to claim 6, is characterized in that, described grapheme material is graphene oxide.
8. a lithium ion battery, it comprises positive pole and negative pole, it is characterized in that, the material of described negative pole comprises: the ferrous carbonate/graphene composite material described in claim 6 or 7, and conductive black, binding agent, wherein, the mass ratio of described ferrous carbonate/graphene composite material, conductive black, binding agent is 7～8: 1～2: 1.
9. ion battery according to claim 8, is characterized in that, described binding agent is Vingon.
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| CN107317019A (en) * | 2017-08-02 | 2017-11-03 | 中国石油大学(华东) | A kind of sodium-ion battery negative pole ferrous carbonate/graphene composite material and preparation method and application |
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| CN108336304A (en) * | 2017-12-27 | 2018-07-27 | 洛阳理工学院 | Hydro-thermal method prepares stainless (steel) wire load FeCO3The method of negative plate |
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