CN103887506A - Cathode material of lithium ion battery, its preparation method and lithium ion battery - Google Patents
Cathode material of lithium ion battery, its preparation method and lithium ion battery Download PDFInfo
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- CN103887506A CN103887506A CN201210556680.6A CN201210556680A CN103887506A CN 103887506 A CN103887506 A CN 103887506A CN 201210556680 A CN201210556680 A CN 201210556680A CN 103887506 A CN103887506 A CN 103887506A
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- lithium ion
- ion battery
- lithium
- nitrite
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010406 cathode material Substances 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 126
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 16
- 125000000962 organic group Chemical group 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 16
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- 238000004140 cleaning Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- -1 organosilane ester Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
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- 238000005108 dry cleaning Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000002071 nanotube Substances 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 claims description 3
- 229960003116 amyl nitrite Drugs 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- APNSGVMLAYLYCT-UHFFFAOYSA-N isobutyl nitrite Chemical compound CC(C)CON=O APNSGVMLAYLYCT-UHFFFAOYSA-N 0.000 claims description 3
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002121 nanofiber Substances 0.000 claims description 3
- 239000002120 nanofilm Substances 0.000 claims description 3
- 150000002826 nitrites Chemical class 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 claims description 3
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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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
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Abstract
The invention provides a cathode material of a lithium ion battery, which comprises a material capable of alloying with lithium, a chemically bonded organic group, and a carbon material capable of coating the material capable of alloying with lithium, and the carbon material can bond with the material capable of alloying with lithium by the organic group through a chemical bond. The invention also provides a preparation method of the cathode material of the lithium ion battery. The cathode material of the present invention can alleviate the large volume expansion and contraction of the material capable of alloying with lithium, simultaneously, the introduced carbon material can increase the conductivity of the integral material; more importantly, compared with the material capable of alloying with lithium and the carbon-coated material prepared by a traditional method, the modified cathode material prepared in the invention enables bonding with the material capable of alloying with lithium and the carbon material through the organic group, strong bonding force of the chemical bond can ensure the stability of the integral cathode material, disconnection generated in electronic conduction network is reduced, so that the electrochemistry performance of the cathode material is increased.
Description
Technical field
The present invention relates to a kind of rechargeable lithium ion batteries, the lithium ion battery that is specifically related to negative material of a kind of high power capacity, stable cycle performance and preparation method thereof and is formed by this negative material.
Background technology
At present, along with growing to high power capacity, long-life batteries demand of mobile electronic equipment, people have higher requirement to the performance of lithium ion battery.Capacity of lithium ion battery is on the low side has become a bottleneck of restriction battery industry development, and finding the positive electrode of height ratio capacity more and negative material has become a developing direction in battery material field.Negative material is the important component part of lithium ion battery, and it is restricting the commercialization process of lithium ion battery, and meanwhile, the development of portable cell and high power capacity electrokinetic cell, has also strengthened the demand for high-energy, high cycle performance negative material.
Along with people are for the continuous exploration of negative material, the material (Si, Sn, Ge, Pb, Sb, Al, Zn etc.) that can form alloy with lithium becomes the most promising class negative material in high-performance lithium ion battery because of its higher theoretical capacity, good embedding/deviate from ability, for example the theoretical capacity of pure silicon material, up to 4200mAh/g, is approximately ten times of graphite cathode.But the cyclical stability of this type of material is poor, cycle life is shorter, and main cause is in charge and discharge cycles process, and huge volumetric expansion, contraction can occur material, if the cubical expansivity of silicon is 300%.Can cause again thus the destruction of conductive network, further worsen the chemical property of material.In addition, can be poor with the common conductivity of the material of lithium alloyage, this is also another key factor that affects its electrical property.
In order to address the above problem, industry mainly adopts nanometer, filming, Composite and designs four kinds of modes of multistage special construction it is carried out to modification at present, but effect is all undesirable, or preparation process complexity, be difficult to realize commercialization, or the introducing of a large amount of inert matters greatly weakened can with the advantage of the material high power capacity of lithium alloyage.
The material of lithium alloyage of volumetric expansion, contraction problem can be huge with to(for) solution, industry generally acknowledges that by its nanometer processing be a kind of effectively solution.Main cause is for reducing 1/2 when particle diameter, and volume is corresponding reduces 1/8, and this is soul-stirring beyond doubt.People adopt respectively high-energy ball milling method, laser method, high-temperature calcination, sol-gel process etc. to prepare nano-powder; Adopt gas-liquid-solid (VLS) growth method, Fabricated by Oxide-assisted Growth Mechanism method, plasma activation method, electrodeposition process etc. to prepare nano wire and nanotube.Its shortcoming is: the dimension that reduces material does not fundamentally solve the problem of the intrinsic volumetric expansion of material, contraction and poorly conductive, and effectively size is difficult to realize as nano particle diameter <10nm.The high surface energy of nano particle also can lure that serious agglomeration occurs storeroom into simultaneously, finally causes battery performance not fully up to expectations.The preparation cost of nanowires/nanotubes is high, the production cycle is long, and nanowire length is limited, is difficult to practical.
The second technical scheme: thin-film material has larger specific area, by material filmization can effectively reduce with film vertical direction on the change in volume that produces, thereby improve the cyclical stability of material.Therefore thin-film material generally has high specific capacity and good cycle performance.The Cui Yi research group of Stanford University has carried out comparatively deep research in silicon thin film field.Its shortcoming is: main chemical vapour deposition technique, magnetron sputtering method, pulsed laser deposition, the vacuum evaporatation etc. of adopting are prepared thin-film material at present, its complicated process of preparation, and cost is higher, is difficult to rapid large-scale and produces, and commercialization process is limited.And the specific area that film is larger causes side reaction and irreversible capacity to increase.
The third technical scheme: main introduce good conductivity, active or nonactive buffering matrix that bulk effect is little by means such as coated, doping, prepare heterogeneous composite negative pole material, thereby volumetric expansion, the contraction of inhibition and lithium alloyage negative material, utilize " buffering skeleton " to carry out the expansion of compensative material.Its roughly can be divided into (1) can with the material of lithium alloyage-nonmetal compound system (be mainly can with the material of lithium alloyage/carbon complex system); (2) can with two kinds of systems of material-metal composite system of lithium alloyage.Need emphasis to be pointed out that, the appearance of the Novel carbon material such as carbon nano-tube (CNT), Graphene (Graphene) in recent years and develop into and can provide more method of modifying, larger hope with the commercial applications of the material of lithium alloyage, above-mentioned material is carried out to compound research and all obtained good progress, but the real practical segment distance in addition of distance.
Its shortcoming is: can with material/metal alloy system of lithium alloyage can improve can with the electric conductivity of the material of lithium alloyage, but still there is breakage of particles and pulverizing problem, limit it and further develop; Can with the material/carbon of lithium alloyage conventional material with carbon elements such as () graphite-like, amorphous carbon classes composite material in conventionally carbon occupy larger proportion, can be less with the content of the material of lithium alloyage, therefore weakened the high power capacity advantage of this material; Can be various with the research method of the composite materials such as the material/CNTs of lithium alloyage (Graphene), but still immature at present.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of lithium ion battery cathode material and its preparation method of modification, the special construction of this negative material can be alleviated and can expand and can stablize again the conductivity that improves material monolithic with the material volume of lithium alloyage, to overcome the deficiencies in the prior art.
Solving the technical scheme that technical problem of the present invention takes is: the negative material that a kind of lithium ion battery is provided, it comprise can with the material of lithium alloyage, the organic group of chemical bonding, and carbon materials that can be coated with the material of lithium alloyage, described carbon materials with can and the material of lithium alloyage between by described organic group with together with chemical bonding, describedly can be selected from Si with the material of lithium alloyage, Sn, Ge, Pb, Sb, Al, the nano particle of a Zn element, nano wire, nanotube, nanofiber, nano film material, or contain Si, Sn, Ge, Pb, Sb, Al, one or more alloy complex in Zn element.
As a further improvement on the present invention, described organic group general formula is-(CH
2)
n-B-(CH
2)
n-, wherein 0≤n≤100, B is the one in aliphat, aromatic series and heterocyclic group.
As a further improvement on the present invention, described carbon materials is selected from as one or more in Graphene, graphene oxide, carbon nano-tube and carbon nano-fiber.
Solving another technical scheme that technical problem of the present invention takes is: a kind of preparation method of negative material of lithium ion battery is provided, comprises the steps:
Step 2, described the first mixed solution is carried out to suction filtration, and with deionized water and absolute ethyl alcohol to suction filtration after gained filter residue repeatedly clean, until filtrate is colourless, then the filter residue after cleaning be dried to processing and obtains powder;
Step 3, by the powder in step 2 with through HF or NH
4f purified solution silica flour after treatment is added in organic solvent, adds subsequently organosilane ester, and under stirring condition, reaction obtains the second mixed solution;
Step 4, the second mixed solution is carried out to suction filtration, and clean to filtrate colourlessly with absolute ethyl alcohol, the then product after dry cleaning, obtains the negative material of described lithium ion battery.
Solving the another technical scheme that technical problem of the present invention takes is: a kind of preparation method of negative material of lithium ion battery is provided, comprises the steps:
Step 2, the product of gained in step 1 is carried out to suction filtration, and clean to filtrate colourlessly with deionized water and absolute ethyl alcohol, then the product after dry cleaning obtains the negative material of described lithium ion battery.
Solving the another technical scheme that technical problem of the present invention takes is: a kind of lithium ion battery is provided, described lithium ion battery comprises anode pole piece, cathode pole piece and electrolyte, the negative material that described cathode pole piece contains the above lithium ion battery or the negative material that contains the lithium ion battery of preparing by above preparation method.
Compared with prior art, the present invention utilizes a step organic chemical reactions or the prepared negative material of two step organic chemical reactionses, not only can alleviate can be huge with the material of lithium alloyage volumetric expansion shrink, the carbon materials of simultaneously introducing can improve the conductivity of material monolithic; What is more important, with utilize that conventional method prepares can be compared with the material/carbon encapsulated material of lithium alloyage, prepared by this method material modified in can and the material of lithium alloyage and carbon materials between by organic group bonding, the powerful adhesion of chemical bond can ensure the stability of material monolithic, reduce to occur disconnecting in electrical conductivity network, further improve the chemical property of material.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is a kind of preparation method's flow chart of the negative material of lithium ion battery of the present invention.
Fig. 2 is another kind of preparation method's flow chart of the negative material of lithium ion battery of the present invention.
Fig. 3 is the synthetic schematic diagram of the negative material of lithium ion battery of the present invention.
Fig. 4 is first three charging and discharging curve figure of the lithium ion battery that forms of the negative material prepared by embodiment mono-.
Fig. 5 is the cycle performance curve chart of the lithium ion battery that forms of the negative material prepared by embodiment mono-and embodiment bis-under 0.2C.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of negative material of lithium ion battery of new modified high power capacity, the conductivity of this negative material and cyclical stability obtain larger raising.The negative material of this lithium ion battery comprises can be with the organic group of the material of lithium alloyage, chemical bonding and by described carbon materials that can be coated with the material of lithium alloyage, described carbon materials with can and the material of lithium alloyage between by described organic group with together with chemical bonding.Wherein, described nano particle, nano wire, nanotube, nanofiber, the nano film material that can be selected from the material of lithium alloyage a kind of element in Si, Sn, Ge, Pb, Sb, Al, Zn, or the alloy complex that contains one or more the above elements; Described organic group general formula is-(CH
2)
n-B-(CH
2)
n-, wherein 0≤n≤100, B is the one in aliphat, aromatic series and heterocyclic group; Described carbon materials is selected from as one or more in Graphene, graphene oxide, carbon nano-tube and carbon nano-fiber.
The present invention also provides a kind of method of preparing the negative material of lithium ion battery by two step organic chemical reactionses, and as shown in Figure 1, it comprises the steps:
Step S01, graphene powder is dissolved in deionized water and carries out ultrasonic dispersion, after being uniformly dispersed, in graphene solution, drip the concentrated hydrochloric acid solution that is dissolved with p-phenylenediamine (PPD), after dropwising, in graphene solution, add natrium nitrosum to react again, and acquisition the first mixed solution that stirs;
Step S02, described the first mixed solution is carried out to suction filtration, and with deionized water and absolute ethyl alcohol to suction filtration after gained filter residue repeatedly clean, until filtrate is colourless, then the filter residue after cleaning be dried to processing and obtains powder;
Step S03, by the powder in step S02 with through HF or NH
4f purified solution silica flour after treatment is added in organic solvent, adds subsequently organosilane ester, and under stirring condition, reaction obtains the second mixed solution;
Step S04, the second mixed solution is carried out to suction filtration, and clean to filtrate colourlessly with absolute ethyl alcohol, the then product after dry cleaning, obtains the negative material of described lithium ion battery.
In described step S01, first adopt improved Hummers method to prepare graphene oxide, then it is reduced, make Graphene.Ultrasonic jitter time is 0.5 ~ 2 hour, and the reaction time is 4 hours.
In described step S02, dry condition is at the temperature of 80 DEG C, to be dried 8 ~ 24 hours in vacuum drying chamber.
In described step S03, the average diameter of silica flour is 100nm, and this organic solvent is at least one in acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, formic acid, acetic acid, pentane, hexane, octane; This organic lipid is at least one in isoamyl nitrite, methyl nitrite, nitrous ether (ethyl nitrite), n-propyl nitrite, Isopropyl Nitrite, butyl nitrite, nitrous acid straight butyl, isobutyl nitrite, nitrite tert-butyl, nitrous acid special butyl ester, octrite, amyl nitrite, nitrites.
In described step S04, dry condition is at the temperature of 80 DEG C, to be dried 8 ~ 24 hours in vacuum drying chamber.
The present invention provides again a kind of method of preparing the negative material of lithium ion battery by a step organic chemical reactions, and as shown in Figure 2, it comprises the steps:
Step S011, by graphene powder with through HF or NH
4silica flour after F solution-treated is added to and in organic solvent, forms mixed solution and carry out ultrasonic dispersion, adds p-phenylenediamine (PPD), then add organosilane ester to react and stir after being uniformly dispersed in described mixed solution, then obtains product;
Step S012, the product of gained in step S011 is carried out to suction filtration, and clean to filtrate colourlessly with deionized water and absolute ethyl alcohol, then the product after dry cleaning obtains the negative material of described lithium ion battery.
In this preparation method, in described step S011, first adopt improved Hummers method to prepare graphene oxide, then it is reduced, make Graphene.Ultrasonic jitter time is 0.5 ~ 2 hour.Chemical time is 6 ~ 20 hours.The average diameter of silica flour is 100nm.This organic solvent is at least one in acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, formic acid, acetic acid, pentane, hexane, octane; This organic lipid is at least one in isoamyl nitrite, methyl nitrite, nitrous ether (ethyl nitrite), n-propyl nitrite, Isopropyl Nitrite, butyl nitrite, nitrous acid straight butyl, isobutyl nitrite, nitrite tert-butyl, nitrous acid special butyl ester, octrite, amyl nitrite, nitrites.
In described step S012, drying condition is at the temperature of 80 DEG C, to be dried 8 ~ 24 hours in vacuum drying chamber.
As shown in Figure 3, Fig. 3 has shown the synthetic schematic diagram of the negative material of lithium ion battery of the present invention, wherein M be can with the material of lithium alloyage.
Illustrate and under different condition, prepare the aspects such as the method for the negative material of lithium ion battery by multiple embodiment below.
Embodiment mono-
First adopt improved Hummers method to prepare graphene oxide, then it is reduced.Gained Graphene (Graphene) 2～8mg is disperseed to 0.5～2h in 40～120mL deionized water for ultrasonic.After being uniformly dispersed, to the concentrated hydrochloric acid solution that drips 20ml in solution and be dissolved with 2～6mmol p-phenylenediamine (PPD), after dropwising, again to the natrium nitrosum that adds 2～6mmol in solution, the reaction time is about 4h, in whole process, stirs always.Finally, the product of gained is carried out to suction filtration, and clean to filtrate with deionized water and absolute ethyl alcohol colourless, then by the product after the cleaning of gained in vacuum drying chamber at 80 DEG C dry 8～24h obtain powder.
By above-mentioned powder and process HF or NH
4f purified solution is processed silica flour 0.01～0.1g rear and that average diameter is about about 100nm and is added in the organic solvent acetonitrile of 5～40ml, adds subsequently appropriate isoamyl nitrite, under stirring condition, reacts 6～20h.The product of gained is carried out to suction filtration, and clean to filtrate with absolute ethyl alcohol colourless, then by the product after the cleaning of gained in vacuum drying chamber at 80 DEG C dry 8～24h obtain the negative material of lithium ion battery.
Embodiment bis-
By according to the obtained Graphene of the method for embodiment 1 (Graphene) 2～8mg with through HF or NH
4f purified solution is processed silica flour 0.01～0.1g rear and that average diameter is about about 100nm and is added ultrasonic 0.5～2h in 40～120ml organic solvent acetonitrile, after being uniformly dispersed, in solution, add 2～6mmol p-phenylenediamine (PPD), after in solution, add appropriate isoamyl nitrite again, under stirring condition, react 6～20h.Finally products therefrom is carried out to suction filtration, and clean to filtrate with deionized water and absolute ethyl alcohol colourless, then by the product after the cleaning of gained in vacuum drying chamber at 80 DEG C dry 8～24h obtain the negative material of lithium ion battery.
Comparative example
Through HF or NH
4the processing of F purified solution, gets rid of the silica flour after surface oxide layer.
Be below specific experiment data comparison and analysis:
In order to test the chemical property of the negative material of preparing according to embodiment mono-and embodiment bis-, test as follows: according to negative material: electrically conductive graphite: sodium carboxymethylcellulose (CMC): the ratio of water=6:2:2:100 is mixed into uniform sizing material, evenly be coated in afterwards on Copper Foil, pole piece is at 120 DEG C more than vacuumize 24h, compressing tablet, is prepared into cathode pole piece.And the cathode pole piece that the negative material of being prepared by embodiment mono-and embodiment bis-is formed is assembled into fastening lithium ionic cell with anode pole piece and electrolyte in the glove box of Ar protection, and carry out chemical property detection.
As shown in Figure 4, Fig. 4 shows that first one section of steeper slope has appearred in negative material prepared by embodiment mono-between 0.6～0.09V, started to occur subsequently the embedding lithium platform of a section very long from 0.09V, embedding lithium capacity is 2337.6mAh/g first, in de-lithium process, it presents the de-lithium slope of a section very long between 0.2～0.58V, and de-lithium capacity is 1519.2mAh/g first; After this negative material, the embedding lithium platform of twice discharge curve is slightly high, about about 0.28V, starting voltage may be corresponding the embedding lithium process of Graphene.The difference compared with first of charging curve for the second time of this material is little, and current potential platform is more approaching, but the embedding lithium platform of charging curve wants shorter relatively for the third time.
As shown in Figure 5, the cyclical stability that can find out the lithium ion battery that contains negative material prepared by embodiment mono-and embodiment bis-from test result is all better, after 50 circulations of lithium ion battery that contain negative material prepared by embodiment mono-, capacity is still maintained at about 570mAh/g, after 50 circulations of lithium ion battery that contain negative material prepared by embodiment bis-at about 396mAh/g, all there is stabilised platform 10 times in Capacitance reserve later.Test data demonstration, the lithium ion battery cyclical stability of the negative material that contains comparative example is the poorest, and it takes off lithium capacity is first 1530mAh/g, and follow-up Capacity fading is very fast, and after 20 circulations, capacity is just down to 279mAh/g.Really there is larger lifting in the lithium ion battery cyclical stability that as can be seen here, contains the negative material after modification.
The present invention utilizes a step organic chemical reactions or the prepared negative material of two step organic chemical reactionses, not only can alleviate can be huge with the material of lithium alloyage volumetric expansion shrink, the carbon materials of simultaneously introducing can improve the conductivity of material monolithic; What is more important, with utilize that conventional method prepares can be compared with the material/carbon encapsulated material of lithium alloyage, prepared by this method material modified in can and the material of lithium alloyage and carbon materials between by organic group bonding, the powerful adhesion of chemical bond can ensure the stability of material monolithic, reduce to occur disconnecting in electrical conductivity network, further improve the chemical property of material.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (13)
1. the negative material of a lithium ion battery, it is characterized in that: it comprise can with the material of lithium alloyage, the organic group of chemical bonding, and carbon materials that can be coated with the material of lithium alloyage, described carbon materials with can and the material of lithium alloyage between by described organic group with together with chemical bonding, describedly can be selected from Si with the material of lithium alloyage, Sn, Ge, Pb, Sb, Al, a kind of nano particle of element in Zn, nano wire, nanotube, nanofiber or nano film material, or describedly can be selected from and contain Si with the material of lithium alloyage, Sn, Ge, Pb, Sb, Al, one or more alloy complex in Zn element.
2. the negative material of lithium ion battery as claimed in claim 1, is characterized in that: described organic group general formula is-(CH
2)
n-B-(CH
2)
n-, wherein 0≤n≤100, B is the one in aliphat, aromatic series and heterocyclic group.
3. the negative material of lithium ion battery as claimed in claim 1, is characterized in that: described carbon materials is selected from as one or more in Graphene, graphene oxide, carbon nano-tube and carbon nano-fiber.
4. a lithium ion battery, it comprises anode pole piece, cathode pole piece and electrolyte, is characterized in that, the negative material that described cathode pole piece contains the lithium ion battery described in claim 1-3 any one.
5. a preparation method for the negative material of lithium ion battery, is characterized in that, comprises the steps:
Step 1, graphene powder is dissolved in deionized water and carries out ultrasonic dispersion, after being uniformly dispersed, in graphene solution, drip the concentrated hydrochloric acid solution that is dissolved with p-phenylenediamine (PPD), then in graphene solution, add natrium nitrosum to react, and acquisition the first mixed solution that stirs;
Step 2, described the first mixed solution is carried out to suction filtration, and with deionized water and absolute ethyl alcohol to suction filtration after gained filter residue repeatedly clean, until the filtrate of gained is colourless after cleaning, then the filter residue after cleaning be dried to processing and obtains powder;
Step 3, by the powder in step 2 with through HF or NH
4the silica flour that F purified solution obtains after processing is added in organic solvent, adds subsequently organosilane ester, and under stirring condition, reaction obtains the second mixed solution;
Step 4, the second mixed solution is carried out to suction filtration obtain filter residue, and it is colourless to the filtrate after cleaning to clean described filter residue with absolute ethyl alcohol, the product then obtaining after dry cleaning, obtains the negative material of described lithium ion battery.
6. preparation method as claimed in claim 5, is characterized in that: in described step 1, ultrasonic jitter time is 0.5 ~ 2 hour.
7. preparation method as claimed in claim 5, is characterized in that: in described step 1, the reaction time is 4 hours.
8. preparation method as claimed in claim 5, is characterized in that: in described step 2, the dry condition of processing is at the temperature of 80 DEG C, to be dried 8 ~ 24 hours in vacuum drying chamber.
9. preparation method as claimed in claim 5, is characterized in that: in described step 3, the average diameter of silica flour is 100nm.
10. preparation method as claimed in claim 5, it is characterized in that: in described step 3, described organic solvent is at least one in acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, formic acid, acetic acid, pentane, hexane, octane.
11. preparation methods as claimed in claim 5, it is characterized in that: in described step 3, described organic lipid is at least one in isoamyl nitrite, methyl nitrite, nitrous ether (ethyl nitrite), n-propyl nitrite, Isopropyl Nitrite, butyl nitrite, nitrous acid straight butyl, isobutyl nitrite, nitrite tert-butyl, nitrous acid special butyl ester, octrite, amyl nitrite, nitrites.
12. preparation methods as claimed in claim 5, is characterized in that: in described step 4, dry condition is at the temperature of 80 DEG C, to be dried 8 ~ 24 hours in vacuum drying chamber.
The preparation method of the negative material of 13. 1 kinds of lithium ion batteries, is characterized in that, comprises the steps:
Step 1, by graphene powder with through HF or NH
4f purified solution silica flour after treatment is added to and in organic solvent, forms mixed solution and carry out ultrasonic dispersion, adds p-phenylenediamine (PPD), then add organosilane ester to react and stir after being uniformly dispersed in described mixed solution, then obtains product;
Step 2, the product of gained in step 1 is carried out to suction filtration obtain filter residue, and it is colourless to the filtrate after cleaning to clean described filter residue with deionized water and absolute ethyl alcohol, then the dry negative material that cleans product afterwards and obtain described lithium ion battery.
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