CN1151570C - Secondary lithium cell having negative pole of carbon with deposited nanometer alloy on its surface - Google Patents

Secondary lithium cell having negative pole of carbon with deposited nanometer alloy on its surface

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Publication number
CN1151570C
CN1151570C CNB001079867A CN00107986A CN1151570C CN 1151570 C CN1151570 C CN 1151570C CN B001079867 A CNB001079867 A CN B001079867A CN 00107986 A CN00107986 A CN 00107986A CN 1151570 C CN1151570 C CN 1151570C
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alloy
carbon
negative pole
nano metal
lithium battery
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CN1327275A (en
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李泓
师丽红
黄学杰
陈立泉
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Institute of Physics of CAS
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Institute of Physics of CAS
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Priority to CNB001079867A priority Critical patent/CN1151570C/en
Priority to PCT/CN2001/000918 priority patent/WO2002027822A1/en
Publication of CN1327275A publication Critical patent/CN1327275A/en
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Publication of CN1151570C publication Critical patent/CN1151570C/en
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/148—Agglomerating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • 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 belongs to the technical field of a secondary lithium battery at room temperature, which provides a secondary lithium battery. The secondary lithium battery is composed of a positive pole, a negative pole, an organic electrolyte solution or polymer electrolyte, etc., wherein the negative pole prepared from a carbon material, and nanometer alloys are deposited on the surface of the carbon material; the carbon material in a composite material is used as a rigid framework; the nanometer alloys are dispersed and pinned on the surface of the carbon material. The secondary lithium battery of the present invention has the advantages of high capacity, good circularity, safety, reliability, heavy current charge and discharge resistance, etc., and is friendly to the environment. The secondary lithium battery of the present invention is suitable for various occasions, such as mobile phones, notebook computers, etc.

Description

A kind of material with carbon element with the surface deposition Nanoalloy is the serondary lithium battery of negative pole
Technical field
The invention belongs to the high-energy battery technical field, particularly the technical field of room temperature serondary lithium battery.
Background technology
In the secondary lithium battery cathode active material, the theoretical specific capacity of lithium metal is 3830mAh/g, and is therefore the highest as the serondary lithium battery energy density of negative active core-shell material with lithium metal.But dendritic growth appears in lithium anode in charge and discharge process, make internal short-circuit of battery, causes battery burning even blast.In order to improve its fail safe, arrive late nineteen eighties at early seventies, lithium alloys such as lithium aluminium, lithium silicon, lithium lead, lithium tin, lithium cadmium once substituted metal lithium are made negative active core-shell material, though this has been avoided the dendritic growth problem to a certain extent, but these alloys can be because volumetric expansion and contraction and efflorescence gradually, i.e. dimension instability in the repeated charge process.Cause the variation that electrically contacts between alloy particle and the collector and between the alloy particle, cause battery performance to degenerate even lost efficacy, as list of references [1]: A Bolahanmu, electrochemistry communication, 138 volumes, 1233 pages, 1993 (K.M.Abraham, Electrochemica.Acta, Vol.138,1233 (1993)) the middle narration.
In 1980, Armand proposes serondary lithium battery can adopt " rocking chair type " battery system (" lithium ion " battery afterwards was otherwise known as), be that the both positive and negative polarity active material all adopts embedding compound (intercalation compounds), this compounds can be reversible storage and exchange lithium ion, thereby avoid using lithium metal or lithium alloy.Initial stage is adopted LiWO 2And Li 6Fe 2O 3Deng embedding compound as negative active core-shell material, but its energy density is too low.Through the effort in 10 years, in March, 1989, Japanese Sony Corporation applied for that employing carbon makes negative active core-shell material, LiCoO 2Make the serondary lithium battery patent of positive electrode active materials, and in 1992 at first with its commercialization, as document [2] Si Kulusa Supreme Being, electrochemistry can will, 139 volumes, 2776 pages, (Bruno Scrosati in 1992, J.Electrochem.Soc, Vol.139,2776 (1992)).
From then on, serondary lithium battery begins to develop rapidly.Petroleum coke, carbon fiber, RESEARCH OF PYROCARBON, native graphite, the material with carbon element of various ways such as Delanium extensively is elected to be the secondary lithium battery cathode active material.
But the graphite-like material with carbon element is lower than 372mAh/g as its specific capacity of negative active core-shell material, still can not satisfy the further pursuit of people to the high-energy density secondary battery.
Recently, our laboratory and some other research group propose to adopt ultra-fine activity/nonactive composite alloy system as negative active core-shell material.The absolute volume of each particle of superfine alloy in charge and discharge process changes less, and the special micro-structural of composite material helps to alleviate change in volume.Therefore compare with the alloy material of large-size, its cyclicity has clear improvement.As document:
[3] Yang Jun, Wen Te, Bei Senhade, solid state ionics, 90 volumes, 281 pages, 1996 (J.Yang, M.Winter, J.O.Besenhard, Solid State Ionics, 90,281 (1996))
[4] hair Europe, Dun Laipu, Ke Teni, Dunne, electrochemistry meeting will, 145 volumes, 4195 pages, (O.Mao, R.A.punlap, I.A.Courtney, J.R. Dahm, J.Electrochem.Soc., 145,4195 (1998) in 1998
[5] Li Hong, yellow-study outstanding person, Chen Liquan, beam forever, Wu Zhengang, electrochemistry can will wall bulletin, 2 volumes, 547 pages, 1999 (H.Li, X.J.Huang, L.Q.Chen, Z.G.Wu, Y.Liang, Electrochem.and Solid-State Lett., 2,547 (1999))
[6] Li Hong, yellow-study outstanding person, Chen Liquan, a kind of is the serondary lithium battery of active material of positive electrode with the nanophase metal material, CN 97112460.4
[7] Li Hong, yellow-study outstanding person, Chen Liquan, a kind of serondary lithium battery, CN 98117759.X
But further studies show that,, in charge and discharge process, can reunite gradually because the superfine alloy negative material has bigger surface energy, form size and reach micron-sized particle, cause its long-term cyclicity variation, the kinetic advantage forfeiture, as list of references [8] Li Hong, yellow-study outstanding person, Chen Liquan, solid state ionics, 2000, (H.Li in the publication, X.J.Huang, L. Q.Chen, SolidState Ionics, 2000, in press) described.
Summary of the invention
The object of the present invention is to provide the serondary lithium battery of a kind of material with carbon element with the surface deposition Nanoalloy as negative pole.In this composite material, material with carbon element provides rigid backbone, can not reunite in charge and discharge process.Simultaneously Nanoalloy disperses to be pinned at carbon material surface, can't contact each other, has the electrode material of this special construction can alleviate Nanoalloy effectively in charge and discharge process reunion.Because material with carbon element and Nanoalloy material are active material, this composite material has very high charge/discharge capacity, has good cycle characteristics and fail safe simultaneously again.And this composite material also has remarkable advantages on dynamics.It is very high to adopt the serondary lithium battery of above-mentioned negative pole to have a capacity, and cyclicity is good, and is safe and reliable, anti-large current density, electrode material cheapness, preparation and remarkable advantage such as environmentally friendly easily.
The main composition of serondary lithium battery of the present invention comprises the carbon negative pole of surface deposition Nanoalloy, contains transition metal oxide positive pole, organic electrolyte solution or the polymer dielectric of lithium.Wherein, separated by barrier film that has soaked organic electrolyte solution or polymer dielectric between positive pole and the negative pole, positive pole is burn-on respectively to go between on collector with an end of negative pole and is linked to each other with the battery case two ends of mutually insulated.
The carbon negative pole of the surface deposition Nanoalloy among the present invention has following characteristics.Material with carbon element is as the core skeleton structure, and its average particle size particle size is 1 μ m to 100 μ m.The alloy of nano-scale is distributed in the surface of material with carbon element, and its particle mean size is that 5nm is to 200nm.The percentage by weight of Nanoalloy and material with carbon element from 10% to 70%.Wherein refer to can reversible embedding and deviate from the carbon of lithium for material with carbon element, mainly comprises the mesocarbon bead, coke, native graphite, Delanium, RESEARCH OF PYROCARBON and carbon fiber and other material with carbon element etc. with electrochemistry capacitance.
In the material with carbon element of the surface deposition Nanoalloy among the present invention, the Nanoalloy of surface deposition can be can also can be with the elemental metals that lithium forms alloy can with the alloy or the heterogeneous alloy that mixes of lithium reaction.Simple substance comprises Sb, Sn, In, Zn, Bi.In the alloy composition of alloy or heterogeneous mixing, contain Sb at least, Sn, In, Zn, five kinds of elements of Bi a kind of.Because Sb behind other element of adding in alloy, Sn, In, Zn, Bi still can be reversible with lithium reaction, therefore allow in the alloy of alloy or heterogeneous mixing, to add all the other metallic elements in the periodic table, but Sb, Sn, In, Zn, five kinds of elements of Bi shared molal quantity sum in alloy is not less than 50%.Because nano metal or alloy ratio are more active, oxidation can take place in its surface inevitably in preparation process, therefore in described Nanoalloy, allow the existence of a small amount of oxygen, but the ratio of all metallic element molal quantity sums of O element and other is not higher than 10%.Metal Sb for example, SnSb alloy, Sn 0.88Sb 0.12[its actual composition may be Sn 0.76With (SnSb) 0.12Two-phase mix, also may be Sn 0.88, Sb 0.12Two-phase mix], Sn 0.44Sb 0.16Cu 0.4, Sn 0.4Zn 0.55O 0.05All meet above-mentioned requirements.And expression formula such as Sn 0.35Cu 0.65, Sn 0.15Sb 0.15Ni 0.55O 0.15The definition that has then exceeded present patent application.
The carbon negative pole of said surface deposition Nanoalloy among the present invention, the implication of surface deposition refers to that the particle of Nanoalloy is dispersed in the surface of carbon granule substantially.The ratio that accounts for the Nanoalloy gross mass of the free Nanoalloy on the carbon granule surface is not higher than 50%.
Negative pole preparation method among the present invention is: the material with carbon element and the conductive additive of surface deposition Nanoalloy are mixed, evenly be mixed and made into the composite material slurries at normal temperatures and pressures with adhesive again.Wherein, conductive additive refers to the material of increase active material conductivity commonly used in the lithium ion battery, as carbon black, and acetylene black, graphite powder, metal powder, wire etc.The percentage by weight of itself and active material is 0% to 15%.Adhesive comprises solution or emulsion.For example, polytetrafluoroethylene is mixed the emulsion that forms with water, Kynoar is dissolved in the solution that cyclohexane forms.Aforesaid composite material slurries are coated in paper tinsel as the various conductions of collector uniformly, net, porous body, the corpus fibrosum material, as Copper Foil, nickel screen, nickel foam is on the carriers such as carbon felt.The gained film thickness is about 20-150 μ m, then film dried down at 100 ℃-150 ℃, and be 20Kg/cm at pressure 2Under compress, continue to be cut into different shape by the prepared cell specification and to be negative pole 100 ℃-150 ℃ bakings 12 hours.
The positive electrode active materials of serondary lithium battery of the present invention is the known material that is used for anode of secondary lithium battery, can reversibly embed and deviate from the transition metal oxide that contains lithium of lithium, and is typical in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide etc.
The organic electrolyte solution of serondary lithium battery of the present invention is the general electrolyte of serondary lithium battery, can be added one or more solvable lithium salts by the mixed solvent that a kind of organic solvent or several organic solvent are formed and form.Typical organic solvent is vinyl carbonate for example, propylene carbonate, diethyl carbonate, dimethyl carbonate, the ethyl-methyl carbonic ester, dimethoxy-ethane etc., typical solvable lithium salts such as lithium perchlorate, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium etc.It is in 1: 1 the vinyl carbonate and diethyl carbonate that typical system is dissolved in volume ratio as 1 mole of lithium hexafluoro phosphate, and it is the medium of 3: 7 vinyl carbonate and dimethyl carbonate that 1 mole of lithium hexafluoro phosphate is dissolved in volume ratio.Polymer dielectric of the present invention is the general polymer dielectric of serondary lithium battery, as contain lithium perchlorate, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, the polyethylene oxygen alkane PEO (poly-ethylene oxide) of lithium salts such as hexafluoroarsenate lithium, polypropylene oxygen alkane PPO (poly-propylene oxide), polyacrylonitrile (PAN) (poly-acrylonitrile), PMMA (poly-methyl methacrylate), polyvinylchloride (poly-vinyl chloride), Kynoar PVDF (poly-vinylidene fluoride) etc.
The barrier film of serondary lithium battery of the present invention is the general barrier film of serondary lithium battery, as the porous polypropylene barrier film, and porous polyethylene barrier film etc.
Serondary lithium battery of the present invention has very high reversible capacity, and cyclicity is good, and is safe and reliable, anti-large current density, and electrode material is cheap, preparation easily, and environmentally friendly.Serondary lithium battery of the present invention is applicable to multiple occasion, mobile phone for example, notebook computer, portable video recorder, electronic toys etc. need the occasion of removable power supply, particularly being applicable to needs higher energy density and than the occasion of high power density, as cordless power tool, and fields such as electric automobile or hybrid vehicle.
The present invention also provides the preparation method of the material with carbon element of surface deposition Nanoalloy, below in conjunction with chart and exemplary embodiments the present invention is done further narration.
Description of drawings
Fig. 1 is other material of button Experimental cell of the present invention, structural representation.
Fig. 2 be in the embodiment of the invention 2 surface deposition the X-ray diffraction pattern figure of mesocarbon bead (MCMB28) of nanometer SnSb alloy.
Fig. 3 is the stereoscan photograph of the MCMB28 of surface deposition nanometer SnSb alloy in the embodiment of the invention 2.
Fig. 4 is with the MCMB28 of the surface deposition nanometer SnSb alloy simulated battery charging and discharging curve as the work electrode active material in the embodiment of the invention 2.
Fig. 5 is with the needle coke of the surface deposition nanometer SnSb alloy charging and discharging curve as the simulated battery of work electrode active material in the embodiment of the invention 9.
Table 1 be embodiment of the invention 1-21 and comparing embodiment Experimental cell discharge and recharge tables of data.
Wherein: 1, stainless steel sealing nut, 2, the polytetrafluoroethylene nut, 3, the stainless steel spring sheet, 4, be the work electrode of active material, 5, porous polypropylene barrier film Celgard with the material with carbon element of surface deposition Nanoalloy 2300 (soaking) through electrolyte, 6, metal lithium sheet is to electrode, 7, for measuring lead.
Embodiment
Embodiment 1
For the material with carbon element of studying surface deposition Nanoalloy of the present invention chemical property, adopt an Experimental cell to study as the serondary lithium battery negative active core-shell material.The Experimental cell structure as shown in Figure 1.Wherein 1 is the stainless steel sealing nut, and 2 is the polytetrafluoroethylene nut, and 3 is the stainless steel spring sheet, and 4 for the material with carbon element with surface deposition nano metal or alloy is the work electrode of active material, and 5 is porous polypropylene barrier film Celgard 2300 (soaking) through electrolyte, 6 be metal lithium sheet to electrode, 7 are the measurement lead. electrolyte is 1 mole of lithium hexafluoro phosphate (LiPF 6) be dissolved in the mixed solvent of vinyl carbonate (EC) and diethyl carbonate (DEC) (volume ratio is 1: 1).
The preparation method of the active material of work electrode is described below in the present embodiment: with SbCl 3And SnCl 2.H 2O is dissolved in the solution that forms 0.5M in the ethylene glycol after by 1: 1 mixed in molar ratio.Being the MCMB2800 (mesocarbon bead, 2800C graphitization) of 10 μ m then with particle mean size, is 9.2: 1 (carbon: alloy) join in the above-mentioned solution and stir by weight percentage.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 20 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer SnSb alloy after the vacuumize, the percentage by weight that dry back Nanoalloy accounts for composite material is 10%.The particle mean size of scanning electron microscope observation SnSb alloy is 60nm, and the ratio that free SnSb alloy accounts for whole alloys is lower than 5%.Products therefrom is lower than 4% through the elementary analysis oxygen content.
With the carbon composite of surface deposition nanometer SnSb alloy is that the work electrode preparation method of active material is described below: with above-mentioned compound carbon dust, mix the formation slurry as the carbon black of conductive additive at normal temperatures and pressures with N-methyl pyrrolidone solution as the Kynoar of binding agent, evenly be coated on the Copper Foil substrate as collector the about 100 μ m of gained film thickness.With the film that obtains at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down.The compound carbon dust in oven dry back, the percentage by weight of carbon black and Kynoar is 90: 5: 5, then film being cut to area is 1cm 2Thin rounded flakes as the composite carbon negative electrode of surface deposition nanometer SnSb alloy, be numbered CNMA1.
With thick 0.4mm, area is 1cm 2Metal lithium sheet as positive pole.
With all battery materials among Fig. 1, except that electrolyte, dry back in the argon filling glove box by the Experimental cell that is assembled into shown in Figure 1.
Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.Current density is 0.1mA/cm 2, the charging cut-ff voltage is 2.0V, discharge cut-off voltage is 0.05V.Discharging and recharging data lists in the table 1.The reversible capacity value is based on negative electrode active material and calculates gained in the table 1, and promptly second all discharge capacities are divided by the quality of negative electrode active material.First numerical table shows the efficiency for charge-discharge in first week in the cyclicity parameter, and promptly the charging capacity in first week is divided by first all discharge capacities.Second number is represented cyclicity, and promptly the charging capacity in the tenth week is divided by first all charging capacitys.
Embodiment 2
Press embodiment 1 described synthetic method, prepare percentage by weight that Nanoalloy accounts for composite material and be 30% carbon composite, the particle mean size of scanning electron microscope observation SnSb alloy is 80nm, and the ratio that free SnSb alloy accounts for whole alloys is lower than 15%.Products therefrom is lower than 2% through the elementary analysis oxygen content.The X-ray diffraction pattern figure of this composite material sees Fig. 2, and its stereoscan photograph is seen Fig. 3.Its structure and pattern have the characteristic feature of this type of carbon/Nanoalloy.
With the compound carbon dust in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, the percentage by weight of carbon black and Kynoar is 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA2.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1, and its charging and discharging curve is seen Fig. 4.This charging and discharging curve is the charging and discharging curve of the graphite-like carbon of typical surface deposition nanometer SnSb alloy.
Embodiment 3
According to embodiment 1 described synthetic method, control reaction temperature is 130 ℃, prepare percentage by weight that Nanoalloy accounts for composite material and be 70% carbon composite, wherein the particle mean size of scanning electron microscope observation SnSb alloy is 200nm, and the ratio that free SnSb alloy accounts for whole alloys is lower than 10%.Products therefrom is lower than 1% through the elementary analysis oxygen content.
With the compound carbon dust in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, the percentage by weight of carbon black and Kynoar is 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA3.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 4
According to being similar to embodiment 1 described synthetic method, with SbCl 3And SnCl 2H 2O is dissolved in the solution that forms 0.05M in the glycerol after by 1: 1 mixed in molar ratio.Being the MCMB2800 (mesocarbon bead, 2800 ℃ of graphitizations) of 1 μ m then with particle mean size, is 9.2: 1 (carbon: alloy) join in the above-mentioned solution and stir by weight percentage.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer SnSb alloy after the vacuumize, the percentage by weight that dry back Nanoalloy accounts for composite material is 10%, the particle mean size of scanning electron microscope observation SnSb alloy is 5nm, and the ratio that free SnSb alloy accounts for whole alloys is lower than 5%.Products therefrom is lower than 10% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, the percentage by weight of carbon black and Kynoar is 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA4.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 5
According to embodiment 1 described synthetic method, prepare percentage by weight that Nanoalloy accounts for composite material and be 40% complex carbon material, the particle mean size of scanning electron microscope observation SnSb alloy is 100nm, the ratio that free SnSb alloy accounts for whole alloys is lower than 10%.Products therefrom is lower than 2% through the elementary analysis oxygen content.With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 (m of the film thickness of gained.The compound carbon dust in oven dry back, the percentage by weight of carbon black and Kynoar is 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA5.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 6
According to embodiment 1 described synthetic method, prepare percentage by weight that Nanoalloy accounts for composite material and be 35% complex carbon material, the particle mean size of scanning electron microscope observation SnSb alloy is 10nm, the ratio that free SnSb alloy accounts for whole alloys is lower than 10%.Products therefrom is lower than 5% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, the percentage by weight of carbon black and Kynoar is 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA6.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 7
Be similar to embodiment 1 described synthetic method, just change MCMB2800 wherein into GPCF28 (2800 ℃ of graphitization asphalt base carbon fibers, average diameter is 10 μ m, long 60-300 μ m, average 100 μ m), obtain percentage by weight that Nanoalloy accounts for composite material and be 30% complex carbon material, the particle mean size of scanning electron microscope observation SnSb alloy is 60nm, and free SnSb alloy accounts for the low son 25% of ratio of whole alloys.Products therefrom is lower than 2% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA7.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 8
Be similar to embodiment 1 described synthetic method, just change MCMB2800 wherein into NG911 (native graphite, particle mean size are 38 μ m), obtain percentage by weight that Nanoalloy accounts for composite material and be 40% complex carbon material.The particle mean size of scanning electron microscope observation SnSb alloy is 100nm, and the ratio that free SnSb alloy accounts for whole alloys is lower than 50%.Products therefrom is lower than 1% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA8.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 9
Be similar to embodiment 1 described synthetic method, just change MCMB2800 wherein into Coke 1200 (1200 ℃ of processing pitch cokes, particle mean size is 60 μ m), obtain percentage by weight that Nanoalloy accounts for composite material and be 35% complex carbon material, the particle mean size of scanning electron microscope observation SnSb alloy is 90nm, and the ratio that free SnSb alloy accounts for whole alloys is lower than 10%.Products therefrom is lower than 1% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA9.
Other material of Experimental cell, structure, assembling and method of testing are with embodiment 1, and charging and discharging curve is seen Fig. 5, is the charging and discharging curve of the lower carbon surface deposition SnSb alloy of typical degree of graphitization.Discharging and recharging data lists in the table 1.
Embodiment 10
Be similar to embodiment 1 described synthetic method, just change MCMB2800 wherein into PS900 (900 ℃, Ar atmosphere pyrolysis sucrose, particle mean size is 10 μ m), the percentage by weight that Nanoalloy accounts for composite material is 40% complex carbon material, the particle mean size of scanning electron microscope observation SnSb alloy is 60nm, and the ratio that free SnSb alloy accounts for whole alloys is lower than 15%.Products therefrom is lower than 2% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA10.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 11
Be similar to embodiment 1 described synthetic method, just change MCMB2800 wherein into PCG28 (artificial coated graphite, particle mean size is 10 μ m), obtain percentage by weight that Nanoalloy accounts for composite material and be 30% complex carbon material, the particle mean size of scanning electron microscope observation SnSb alloy is 50nm, and the ratio that free SnSb alloy accounts for whole alloys is lower than 10%.Products therefrom is lower than 3% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA11.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 12
The preparation method of work electrode active material is described below: with SbCl 3Being dissolved in the glycerol solution that forms 0.5M, is that the MCMB2800 (mesocarbon bead, 2800 ℃ of graphitizations) of 10 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer Sb metal after the vacuumize, to account for the percentage by weight of composite material be 30% to Nanoalloy in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation Sb is 80nm, and the ratio that free Sb accounts for whole Sb is lower than 10%.Products therefrom is lower than 1% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly applies on the sub-Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA12.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 13
The preparation method of work electrode active material is described below: with SnCl 2.H 2O is dissolved in the solution that forms 0.1M in the glycerol ethylene glycol.Be that the MCMB2800 of 25 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer Sn metal after the vacuumize, to account for the percentage by weight of composite material be 50% to Nanoalloy in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation Sn is 150nm, and the ratio that free Sn accounts for whole Sn is lower than 5%.Products therefrom is lower than 1% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA13.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 14
The preparation method of work electrode active material is described below: with SbCl 3, InCl 3By being dissolved in the solution that forms 0.5M in the ethylene glycol after 1: 1 the mixed in molar ratio.Be that the MCMB2800 of 25 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer InSb metal after the vacuumize, to account for the percentage by weight of composite material be 30% to Nanoalloy in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation InSb is 60nm, and the ratio that free InSb accounts for whole InSb is lower than 5%.Products therefrom is lower than 1% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA14.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 15
The preparation method of work electrode active material is described below: with SbCl 3Be dissolved in the solution that forms 0.5M in the ethylene glycol.Be that the MCMB2800 of 25 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 150% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer SbZn/Sb alloy [mol ratio of Sb and Zn is 2: 1] after the vacuumize, to account for the percentage by weight of composite material be 40% to Nanoalloy in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation SbZn/Sb alloy is 80nm, and the ratio that free SbZn/Sb alloy accounts for whole SbZn/Sb alloys is lower than 5%.Products therefrom is lower than 4% through the elementary analysis oxygen content.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA15.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 16
The preparation method of work electrode active material is described below: with ZnCl 2Be dissolved in the solution that forms 0.05M in the glycerol.Be that the MCMB2800 of 25 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Mg powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nano metal Zn after the vacuumize, to account for the percentage by weight of composite material be 30% to Nanoalloy in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation Zn is 150nm, and the ratio that free Zn accounts for whole Zn is lower than 5%.It is Zn that elementary analysis records the product chemical formula 0.9Mg 0.07O 0.03
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA16.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 17
The preparation method of work electrode active material is described below: with SnCl 2H 2O, CuCl 2By being dissolved in the solution that forms 0.5M in the ethylene glycol after 1: 1 the mixed in molar ratio.Be that the Coke 1200 of 60 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains Coke 1200 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain surface deposition nanometer Cu after the vacuumize 6Sn 5The carbon composite sample of alloy, to account for the percentage by weight of composite material be 30% to Nanoalloy in the compound carbon dust in dry back, and the particle mean size of scanning electron microscope observation Nanoalloy is 80nm, and the ratio that free Nanoalloy accounts for whole Nanoalloys is lower than 5%.It is Cu that elementary analysis records the product chemical formula 0.4Sn 0.33Zn 0.20O 0.07
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA17.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 18
The preparation method of work electrode active material is described below: with SnCl 2.H 2O, SbCl 3By being dissolved in the solution that forms 0.5M in the ethylene glycol after 2: 3 the mixed in molar ratio.Be that the MCMB2800 of 25 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nano metal or alloy after the vacuumize, to account for the percentage by weight of composite material be 35% to Nanoalloy in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation Nanoalloy is 80nm, and the ratio that free Nanoalloy accounts for whole Nanoalloys is lower than 5%.It is Sn that elementary analysis records the product chemical formula 0.35Sb 0.65Zn 0.88O 0.02
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA18.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 19
The preparation method of work electrode active material is described below: with InCl 3Be dissolved in the solution that forms 0.1M in the glycerol.Be that the MCMB2800 of 25 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer In metal after the vacuumize, to account for the percentage by weight of composite material be 50% to Nanoalloy in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation nanometer In metal is 80nm, and the ratio that free nanometer In metal accounts for whole nanometer In metals is lower than 5%.Record the product oxygen content and be lower than 1%.
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA19.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 20
The preparation method of work electrode active material is described below: with SnCl 2.H 2O, FeCl 3By being dissolved in the solution that forms 0.5M in the ethylene glycol after 2: 1 the mixed in molar ratio.Be that the Coke 1200 of 60 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer Sn/SnFe alloy after the vacuumize, to account for the percentage by weight of composite material be 30% to Nanoalloy in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation nanometer Sn/SnFe alloy is 100nm, and the ratio that free nanometer Sn/SnFe alloy accounts for whole nanometer Sn/SnFe alloys is lower than 5%.It is Sn that elementary analysis records the product chemical formula 0.7Fe 0.25O 0.05
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA20.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Embodiment 21
The preparation method of work electrode active material is described below: with BiCl 3Be dissolved in the solution that forms 0.5M in the ethylene glycol.Be that the MCMB2800 of 25 μ m joins in the above-mentioned solution and stirs then with particle mean size.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0-3 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain the carbon composite sample of surface deposition nanometer Bi metal after the vacuumize, to account for the percentage by weight of composite material be 30% to nano metal Bi in the compound carbon dust in dry back, the particle mean size of scanning electron microscope observation nano metal Bi is 100nm, and the ratio that free nano metal Bi accounts for whole nano metal Bi is lower than 5%.It is Bi that elementary analysis records the product chemical formula 0.98O 0.02
With the complex carbon material in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.The compound carbon dust in oven dry back, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered CNMA21.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
[comparing embodiment one]
Be similar to embodiment 1 described synthetic method, with SbCl 3And SnCl 2.H 2O is dissolved in the solution that forms 0.5M in the ethylene glycol after by 1: 1 mixed in molar ratio.The Zn powder is joined in the solution that contains MCMB2800 than slowly by 95% metering, and high-speed stirred simultaneously.Reaction temperature is controlled at 0 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain nanometer SnSb alloy sample after the vacuumize.The particle mean size of scanning electron microscope observation SnSb alloy is 70nm, and products therefrom is lower than 2% through the elementary analysis oxygen content.
With the nanometer SnSb alloy in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.Oven dry back nanometer SnSb alloy, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered SnSb.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
[comparing embodiment two]
Be similar to embodiment 1 described synthetic method, with SbCl 3Be dissolved in the solution that forms 0.5M in the glycerol.With the Zn powder by 95% metering than slowly adding in the solution, and high-speed stirred simultaneously.Reaction temperature is controlled at 0 ℃.At last, clean with ethanol behind the sedimentation and filtration of black, promptly obtain nanometer Sb metal sample after the vacuumize.The particle mean size of scanning electron microscope observation nanometer Sb metal is 100nm, and products therefrom is lower than 2% through the elementary analysis oxygen content.
With the nanometer Sb metal in this example, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.Oven dry back nanometer Sb metal, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered Sb.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
[comparing embodiment three]
With MCMB2800, carbon black mixes the formation slurry at normal temperatures and pressures with the N-methyl pyrrolidone solution of Kynoar, evenly is coated on the Copper Foil substrate the about 100 μ m of the film thickness of gained.Oven dry back MCMB2800, carbon black and Kynoar percentage by weight are 90: 5: 5, all the other work electrode preparation processes are with embodiment 1.Work electrode is numbered MCMB.
Other material of Experimental cell, structure, assembling and method of testing discharge and recharge data and list in the table 1 with embodiment 1.
Table 1:
With the material with carbon element of surface deposition nano metal or the alloy numbering as the working electrode of active material The component of the material with carbon element of surface deposition nano metal or alloy and proportion thereof The electrochemical properties of corresponding simulated battery Corresponding embodiment numbering
In the composite material as the material with carbon element of skeleton Metal or alloy in the composite material Adhere to alloy and account for the ratio of whole alloys The percentage by weight of alloy in material Reversible capacity (MAH/gram) Cyclicity parameter (%)
Kind Particle mean size (μ m) Composition expression formula after the elementary analysis Particle mean size (nm)
CNMA1 MCMB28 10 Sn 0.48Sb 0.48O 0.04 60 95 10 330 88，99 1
CNMA2 MCMB28 6 Sn 0.48Sb 0.50O 0.02 80 85 30 420 84，98 2
CNMA3 MCMB28 10 Sn 0.48Sb 0.50O 0.01 200 90 70 668 70，92 3
CNMA4 MCMB28 1 Sn 0.48Sb 0.47O 0.1 5 95 25 431 85，99 4
CNMA5 MCMB28 10 Sn 0.48Sb 0.50O 0.02 100 90 40 510 73，96 5
CNMA6 MCMB28 10 Sn 0.47Sb 0.48O 0.05 10 90 35 484 74，94 6
CNMA7 GPCF28 100(L)， 10(D) Sn 0.38Sb 0.6O 0.02 60 75 30 437 72，88 7
CNMA8 NG911 38 Sn 0.3Sb 0.69O 0.01 100 50 40 482 76，94 8
CNMA9 Coke 1200 60 Sn 0.48Sb 0.51O 0.01 90 90 35 366 76，98 9
CNMA10 PS 900 10 Sn 0.49Sb 0.49O 0.02 60 85 40 610 70，91 10
CNMA11 PCG28 10 Sn 0.485Sb 0.485O 0.03 50 90 30 458 75，95 11
CNMA12 MCMB28 10 Sb 0.99O 0.01 80 90 70 552 65，85 12
CNMA13 MCMB28 25 Sn 0.99O 0.01 150 95 50 647 90，85 13
CNMA14 MCMB28 25 In 0.495Sb 0.495O 0.01 60 95 30 414 82，87 14
CNMA15 MCMB28 25 Sb 0.64Zn 0.32O 0.04 80 95 40 422 78，90 15
CNMA16 MCMB28 25 Zn 0.9Mg 0.07O 0.03 150 95 30 327 78，85 16
CNMA17 Coke 1200 60 Cu 0.4Sn 0.33Zn 0.20O 0.07 80 95 30 277 70，80 17
CNMA18 MCMB28 25 Sn 0.35Sb 0.65Zn 0.08O 0.02 80 95 35 454 78，95 18
CNMA19 MCMB28 25 In 0.99O 0.01 100 95 50 500 70，88 19
CNMA20 MCMB28 25 Sn 0.7Fe 0.25O 0.05 80 95 30 680 72，85 20
CNMA21 MCMB28 25 Bi 0.99O 0.01 100 90 30 330 85，95 21
SnSb / / Sn 0.49Sb 0.49O 0.02 70 / / 720 70，85 Than 1
Sb / / Sb 0.99O 0.02 100 / / 620 65，75 Than 2
MCMB MCMB28 10 / / / / 320 92，99 Than 3

Claims (4)

1, a kind of material with carbon element with surface deposition nano metal or alloy is the serondary lithium battery of negative pole, comprise negative pole, the transition metal oxide positive pole that contains lithium, organic electrolyte solution or polymer dielectric, separate by barrier film that has soaked organic electrolyte solution or polymer dielectric between positive pole and the negative pole, positive pole is burn-on respectively to go between on collector with an end of negative pole and is linked to each other with the battery case two ends of mutually insulated, and it is characterized in that: used negative pole is that the material with carbon element of surface deposition nano metal or alloy is made;
Wherein material with carbon element is a core skeleton, and its average particle size particle size is 25 μ m to 100 μ m;
Nano metal or alloy mainly are distributed in the surface of material with carbon element, and its particle mean size is that 5nm is to 200nm;
The percentage by weight of nano metal or alloy and material with carbon element from 10% to 70%;
Described surface deposition nano metal or alloy are elemental metals or alloy, and elemental metals comprises Sb, Sn, In, Zn, Bi; In the composition of alloy, contain Sb at least, Sn, In, Zn, five kinds of elements of Bi a kind of, and Sb, Sn, In, Zn, five kinds of elements of Bi shared molal quantity sum in alloy is not less than 50%.
2, be the serondary lithium battery of negative pole by the described material with carbon element with surface deposition nano metal or alloy of claim 1, it is characterized in that: described material with carbon element is mesocarbon bead, coke, native graphite, Delanium, RESEARCH OF PYROCARBON or carbon fiber.
3, by being the serondary lithium battery of negative pole by the described material with carbon element of claim 1 with surface deposition nano metal or alloy, it is characterized in that: add a small amount of oxygen in nano metal that can also be therein or the alloy, but the ratio of all metallic element molal quantity sums of oxygen element and other is not higher than 10%.
4, by being the serondary lithium battery of negative pole by the described material with carbon element with surface deposition nano metal or alloy of claim 1, it is characterized in that: wherein the ratio that accounts for nano metal or alloy gross mass of free nano metal or the alloy on the carbon granule surface is not higher than 50%.
CNB001079867A 2000-06-06 2000-06-06 Secondary lithium cell having negative pole of carbon with deposited nanometer alloy on its surface Expired - Lifetime CN1151570C (en)

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