CN101908618A - Anode material for lithium-ion secondary battery and manufacture method thereof and lithium rechargeable battery - Google Patents

Anode material for lithium-ion secondary battery and manufacture method thereof and lithium rechargeable battery Download PDF

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CN101908618A
CN101908618A CN2010101963713A CN201010196371A CN101908618A CN 101908618 A CN101908618 A CN 101908618A CN 2010101963713 A CN2010101963713 A CN 2010101963713A CN 201010196371 A CN201010196371 A CN 201010196371A CN 101908618 A CN101908618 A CN 101908618A
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lithium
negative electrode
ion secondary
secondary battery
electrode active
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佐藤俊树
铃木顺
桂翔生
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Kobe Steel Ltd
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Kobe Steel Ltd
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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
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a kind of deterioration that has high charge/discharge capacity and can improve the negative electrode active material of following charge and discharge cycles, and can be with anode material for lithium-ion secondary battery and manufacture method thereof that discharges and recharges at a high speed and the lithium rechargeable battery that uses this anode material for lithium-ion secondary battery.The anode material for lithium-ion secondary battery (10) that is used for lithium rechargeable battery of the present invention is characterised in that, anode material for lithium-ion secondary battery (10) is gone up formation negative electrode active material (2) at negative electrode collector (1) and is formed, and described negative electrode active material (2) is to disperse the Sn of 1～40at% and at least a metal that is selected from 4A, 5A, the 6A family element of 3～20at% to form in amorphous carbon.

Description

Anode material for lithium-ion secondary battery and manufacture method thereof and lithium rechargeable battery
Technical field
The present invention relates to be used for lithium rechargeable battery anode material for lithium-ion secondary battery and manufacture method thereof, use the lithium rechargeable battery of this anode material for lithium-ion secondary battery.
Background technology
In recent years, because the miniaturization and the high performance of portable equipment, more and more higher to the requirement of the energy density of the secondary cell that carries.Wherein, lithium rechargeable battery is compared with NI-G secondary cell or nickel-hydrogen secondary cell, shows high voltage, high charge/discharge capacity (energy density), and therefore, beginning is extensive use of as the power supply of above-mentioned portable equipment.
The electrolyte that lithium rechargeable battery mainly moves by negative material, positive electrode, with the isolated material of these electrode materials insulation, electric charge between auxiliary electrode material, the battery case of accommodating these constitute.And anode material for lithium-ion secondary battery is made of the material of coating negative electrode active material on as the Copper Foil of current-collecting member or copper alloy foil, and as negative electrode active material, using graphite usually is material with carbon element.But, reach theoretical capacity (372mAh/g) because graphite is the discharge capacity of material with carbon element, so pursue higher discharge capacity and charging capacity.
Therefore, as the negative electrode active material that shows high charge/discharge capacity, can study with the metal of lithium alloyage Si, Ge, Ag, In, Sn and Pb etc.For example in patent documentation 1 motion will show that graphite is the negative material of Sn evaporation when the collector body surface of the so theoretical charge/discharge capacity of the general 2.5 times 993mAh/g of material with carbon element.But, because Sn (with the alloying of lithium, the release of lithium) when the discharging and recharging of lithium ion repeats volumetric expansion and contraction, thus, Sn peels off and the resistance increase from collector body, or Sn self breaks and cause the contact resistance between the Sn to increase, therefore, the result exists charge/discharge capacity to reduce such problem significantly.
As the scheme that addresses this problem, in order to relax the change in volume of negative electrode active material, for example in patent documentation 2 motion with the surface of metallic nanocrystalline such as Sn carry out the metallic nanocrystalline complex of carbon coating, maybe will mix with Kynoar bond materials such as (PVDF) and carbon black with the metallic nanocrystalline complex of carbon overlay binding metallic nanocrystalline complex and be coated on the copper collector after, carry out the negative material that vacuum-sintering forms.
Patent documentation 1: TOHKEMY 2002-110151 communique
Patent documentation 2: TOHKEMY 2007-305569 communique
But, in existing technology, have problem as follows.
In the negative material of patent documentation 2, because the metallic crystal of occlusion lithium is a nano-scale, so the change in volume that the lithium occlusion causes is little, can improve charge/discharge capacity, but in order to use bond material to carry out combination between the metallic nanocrystalline complex, even added carbon black, also can variation as the conductivity of negative electrode material.Therefore, in the purposes that needs carry out discharging and recharging at a high speed as automobile, existence can not be flow through big electric current, and charge/discharge capacity reduces such problem.
Summary of the invention
The present invention is the invention of finishing in view of above-mentioned problem, a kind of deterioration that has high charge/discharge capacity and can improve the negative electrode active material of following charge and discharge cycles is provided, and can be with the anode material for lithium-ion secondary battery that discharges and recharges at a high speed and manufacture method thereof and the lithium rechargeable battery that uses anode material for lithium-ion secondary battery.
As the method that is used to solve above-mentioned problem, the invention provides a kind of anode material for lithium-ion secondary battery, it is used for lithium rechargeable battery, it is characterized in that, described anode material for lithium-ion secondary battery forms negative electrode active material and forms on negative electrode collector, described negative electrode active material is to disperse at least a metal in 4A, 5A, the 6A family element (following be fit to be called 4A, 5A, 6A family element) that is selected from of the Sn of 1～40at% and 3～20at% to form in amorphous carbon.
According to such formation, Sn does not carry out alloying with carbon and is dispersed in the amorphous carbon with nano-particles size, and on the other hand, 4A, 5A, 6A family element combine with carbon, is dispersed in the amorphous carbon as the carbide of nano-particles size.And Sn is by the sp in the crystal structure of amorphous carbon 3In conjunction with suppressing the volumetric expansion that the lithium occlusion causes.Therefore, when improving charge/discharge capacity (relative quality capacity or relative volume capacity), cycle characteristics (even the circulation negative electrode active material that repeats to discharge and recharge can deterioration yet (peel off, come off etc.), the character that charge/discharge capacity does not reduce) improve.On the other hand, owing to be dispersed in 4A, the 5A in the amorphous carbon, the carbide conductivity height of 6A family element, therefore, the conductivity of film improves.Therefore, even electronics flows easily in big electric current, also can discharge and recharge at a high speed.
The present invention is on the basis of first invention, the manufacture method of anode material for lithium-ion secondary battery is provided, it is characterized in that, by vapour deposition process, on negative electrode collector, form the Sn of 1～40at% and at least a metal that is selected from 4A, 5A, the 6A family element of 3～20at% and be scattered in the negative electrode active material that forms in the amorphous carbon.
According to such manufacture method, use vapour deposition process, Sn effectively disperses in amorphous carbon, and simultaneously, 4A, 5A, 6A family element are dispersed in the amorphous carbon as carbide.In addition, the control that the metal of amorphous carbon and regulation is formed or the control by film thickness of negative electrode active material become easily, can make easy and easy the carrying out of formation of the negative electrode active material on negative electrode collector.
In addition, the manufacture method of anode material for lithium-ion secondary battery of the present invention is characterized in that, uses graphite target, forms the amorphous carbon of described negative electrode active material by the arc ion plating method.
According to such manufacture method, can make film forming speed realize thick filmization soon, in addition, by forming the many films of graphite structure, easy occlusion lithium.
Lithium rechargeable battery of the present invention is characterized in that, uses the anode material for lithium-ion secondary battery of first invention.
According to such formation, the anode material for lithium-ion secondary battery of the application of the invention can form and has high charge/discharge capacity, cell excellent in cycle characteristics and the lithium rechargeable battery that can discharge and recharge at a high speed.
According to anode material for lithium-ion secondary battery of the present invention, owing to have high charge/discharge capacity and the deterioration of the negative electrode active material of charge and discharge cycles is followed in improvement, thus can be manufactured on lithium rechargeable battery also good on the cycle characteristics.And, improve by conductivity, also can discharge and recharge at a high speed.
According to the manufacture method of anode material for lithium-ion secondary battery of the present invention, in negative electrode active material, the Sn of 1～40at% and at least a metal that is selected from 4A, 5A, the 6A family element of 3～20at% effectively can be scattered in the amorphous carbon.In addition, can easily carry out the control of composition of amorphous carbon and these metals or negative electrode active material by the control of film thickness, negative electrode active material is formed on the negative electrode collector easily and easily.
In addition, by using the arc ion plating method of graphite target, can realize thick filmization, and can form the film of easy occlusion lithium.
Lithium rechargeable battery of the present invention has high charge/discharge capacity, and is good and can discharge and recharge at a high speed on cycle characteristics.
Description of drawings
Fig. 1 is the profile that schematically shows the formation of anode material for lithium-ion secondary battery of the present invention;
Fig. 2 is the schematic diagram that is used to make the sputter equipment of anode material for lithium-ion secondary battery of the present invention;
Fig. 3 is the schematic diagram that is used to make the AIP-sputter set composite of anode material for lithium-ion secondary battery of the present invention;
Fig. 4 is a schematic diagram of representing the structure of the evaluation electricity pool unit that uses in an embodiment.
Among the figure: 1-negative electrode collector, 2-negative electrode active material, 10-anode material for lithium-ion secondary battery (negative material).
Embodiment
Then, with reference to accompanying drawing anode material for lithium-ion secondary battery of the present invention and manufacture method thereof and lithium rechargeable battery are elaborated.
" anode material for lithium-ion secondary battery "
As shown in Figure 1, anode material for lithium-ion secondary battery of the present invention (following be fit to be called negative material) 10 has negative electrode collector 1, is formed on the negative electrode active material 2 on the negative electrode collector 1, and negative electrode active material 2 is that the Sn of 1～40at% is dispersed in material in the amorphous carbon as at least a metal in 4A, 5A, the 6A family element (following be fit to be called 4A, 5A, 6A family element) that is selected from of metal nanoparticle, 3～20at% as the carbide nanometer particle.
Below, each formation is described.
＜negative electrode collector 〉
The material of negative electrode collector 1 need have the mechanical property of the stress of tolerance negative electrode active material 2 expansions.In big (plastic deformation is easy, endurance the is little) material that stretches, follow the expansion of negative electrode active material 2, produce stretching (plastic deformation) together, and produce fold or bending etc.From such reason, as the material of negative electrode collector 1, generally use metals such as copper, copper alloy, nickel, stainless steel, wherein, from easily concerning this point of processing film and cost point, preferred endurance is big, such Copper Foil or copper alloy foil below 2% degree that is stretched as ruptures.In addition, tensile strength is high more then good more, is preferably 700N/mm at least 2Above tensile strength.In this, compared with the more preferably rolling copper alloy foil of electrolytic copper foil.As high-intensity like this copper alloy foil, for example can enumerate the paper tinsel that uses the gloomy series copper alloy of so-called section that contains Ni or Si.
The thickness of negative electrode collector 1 is preferably 1～50 μ m.When thickness less than 1 μ m, negative electrode collector 1 can not tolerate the stress when negative electrode collector 1 surface formation negative electrode active material 2, may produce fracture or be full of cracks on negative electrode collector 1.On the other hand, when thickness surpassed 50 μ m, manufacturing cost increased, and in addition, battery may maximize.In addition, be more preferably 5～20 μ m.
＜negative electrode active material 〉
[amorphous carbon]
Amorphous carbon has the sp of carbon 2And sp 3In conjunction with, for example show the crystal structure that diamond-like-carbon is such.The sp of the carbon in the above-mentioned structure 3In conjunction with the effect of playing the change in volume that is scattered in the metal in the amorphous carbon when suppressing to discharge and recharge.In addition, increase this point from charge/discharge capacity, amorphous carbon preferably has the structure of the lithium of occlusion graphite structure etc.
[Sn and be selected from least a metal in 4A, 5A, the 6A family element]
Sn consists of 1～40at%, is selected from the 3～20at% that consists of of at least a metal in 4A, 5A, the 6A family element.
Because Sn is a low-melting metal can be with lithium alloyage the time, so be scattered in the amorphous carbon with the high non-alloying of carbon of fusing point.In addition, 4A, 5A, 6A family element are the metals of making intermetallic compound with Sn, exist under the situation of carbon, and major part does not combine with Sn and combines the formation carbide with carbon, is scattered in the amorphous carbon.Therefore, form in amorphous carbon the structure of nano particle of the carbide of the metal nanoparticle that disperses Sn, 4A, 5A, 6A family element.
Be dispersed in the amorphous carbon by Sn and (be separated into the nanometer crystal druse shape) 1～40at%, compare with the negative material that coating graphite on negative electrode collector forms, it is good to form charge/discharge capacity (relative quality capacity or relative volume capacity), and cycle characteristics does not have the negative material 10 of deterioration.In addition, the metal as increasing the relative quality capacity has Si and Sn, and the metal as increasing the relative volume capacity has Si, Ag, In, Sn and Bi.
On the other hand, by 4A, 5A, 6A family element (being the carbide of 4A, 5A, 6A family element) are dispersed in the amorphous carbon and (are separated into the nanometer crystal druse shape), conductivity (electron conduction) improves.That is, because these carbide conductivity height discharge and recharge at a high speed so can form the conductive path of electronics.
Sn content in the negative electrode active material 2 is 1～40at%.By adding Sn, can realize the raising of charge/discharge capacity and cycle characteristics, particularly by content being set in this scope, charge/discharge capacity further increases, in addition, even after discharging and recharging repeatedly, owing to can relax the change in volume of Sn by the carbon matrix, so can obtain good cycle characteristics.When Sn contained quantity not sufficient 1at%, the effect that increases charge/discharge capacity reduced.In addition, in order further to improve charge/discharge capacity, be preferably more than the 5at%, more preferably more than the 10at%.On the other hand, when the content of Sn surpasses 40at%, can not the change in volume of Sn be relaxed by the carbon matrix, though initial stage charge/discharge capacity height, membrane structure destroys and the bigger reduction of cycle characteristics.In addition, in order further to improve cycle characteristics, be preferably below the 35at%, more preferably below the 30at%.
The content of 4A, 5A, 6A family element is 3～20at%.
4A, 5A, 6A family element contain quantity not sufficient 3at% the time, conductivity can not improve, and can not discharge and recharge at a high speed.On the other hand, when surpassing 20at%, the ratio of carbide increases, and therefore suppresses the diffusion of the lithium atom in the negative electrode active material, therefore, can not discharge and recharge at a high speed.
At this, the particle diameter that is scattered in the Sn in the amorphous carbon is preferably 0.5～100nm.By particle size dispersion is the nanometer crystal druse shape of 0.5～100nm, and the change in volume of the metal when discharging and recharging is further relaxed.In addition, the particle diameter of the carbide of 4A, 5A, 6A family element is preferably 2～30nm.If particle diameter is that then conductivity improves easily more than the 2nm, if be that 30nm is with the next diffusion that is difficult to hinder lithium.
The control of the particle diameter of the carbide of such Sn or 4A, 5A, 6A family element is undertaken by the carbon in the control negative electrode active material 2 and the composition of these metals.In addition, the control of composition can the membrance casting condition when forming negative electrode active material 2 on negative electrode collector 1 be controlled.In addition, the mensuration of the particle diameter of the carbide of such Sn or 4A, 5A, 6A family element can be by to observe with FIB-TEM or the full width at half maximum of the diffracted ray intensity of the metal that film X (Ai Kesi) x ray diffraction is observed is that carry out on the basis.And the analysis that these metals are formed can be undertaken by Auger electron spectroscopy analysis (AES analysis).
" manufacture method of anode material for lithium-ion secondary battery "
The manufacture method of anode material for lithium-ion secondary battery 10 of the present invention is, the Sn of 1～40at% and at least a metal (carbide of metal) that is selected from 4A, 5A, the 6A family element of 3～20at% are scattered in the negative electrode active material 2 that forms in the amorphous carbon, are formed on the negative electrode collector 1 by vapour deposition process.
The manufacture method of negative material 10 comprises negative electrode collector and forms operation and negative electrode active material formation operation, behind negative electrode collector formation operation formation negative electrode collector 1, form operation by negative electrode active material, the Sn of 1～40at% and the carbide that is selected from least a metal in 4A, 5A, the 6A family element of 3～20at% are scattered in the negative electrode active material 2 that forms in the amorphous carbon, are formed on this negative electrode collector 1 by vapour deposition process.
Below, each operation is described.
＜negative electrode collector forms operation 〉
Negative electrode collector forms operation for forming the operation of negative electrode collector 1.That is, be the operation of preparing negative electrode collector 1 in order to form negative electrode active material 2.As negative electrode collector 1, as mentioned above, as long as use known negative electrode collector 1.In addition, form operation, can implement the correction of distortion of negative electrode collector 1 or grinding etc. by negative electrode collector.
＜negative electrode active material forms operation 〉
It is with the Sn of 1～40at% and the carbide that is selected from least a metal in 4A, 5A, the 6A family element of 3～20at% that negative electrode active material forms operation, be scattered in the amorphous carbon by vapour deposition process, simultaneously, negative electrode active material 2 as the dispersion by Sn in above-mentioned amorphous carbon or carbide forms is formed on the operation on the negative electrode collector 1.
By using vapour deposition process, with the Sn of 1～40at% and the carbide that is selected from least a metal in 4A, 5A, the 6A family element of 3～20at%, be scattered in the amorphous carbon with the nanometer crystal druse shape, simultaneously, can on negative electrode collector 1, form negative electrode active material 2.In addition, the composition of amorphous carbon and Sn or 4A, 5A, 6A family element freely can be controlled in the wide scope, simultaneously, also can easily control, negative electrode active material 2 is formed on the negative electrode collector 1 easily and easily by film thickness.
In addition, in manufacture method of the present invention, owing to use vapour deposition process, therefore, make carbide with Sn or 4A, 5A, 6A family element be dispersed in the film that forms in the amorphous carbon and be formed on by evaporation and obtain negative material 10 on the negative electrode collector 1.Therefore, can omit in the present manufacture method, with graphite matter carbon dust be coated on operation on the negative electrode collector, make coating powder for drying operation and will be coated with and dry powder improves the operation of density by being pressed in negative electrode collector.
As vapour deposition process, can use chemical vapour deposition technique (CVD:Chemical VaporDeposition method) or physical vaporous deposition (PVD:Physical Vapor Deposition method) etc., as the CVD method plasma CVD method is arranged, vacuum vapour deposition, sputtering method, ion plating method, arc ion plating method (AIP), laser ablation method etc. are arranged as the PVD method.When particularly needing thick film, need to use the fast gimmick of film forming speed, to this, the AIP method is effective.For example, if target is carried out arc discharge as graphite, then graphite by arc discharge heat and as carbon atom or ion evaporation, can be at negative electrode collector surface sediment amorphous carbon.And then, in the AIP method of using graphite target, because except that carbon atom or ion that arc discharge produces from target material surface, particulate (macroparticle) from number μ m to the graphite of tens of μ m also can fly out and pile up at negative electrode collector, therefore, compare with sputtering method or ion plating method, can form the many films of graphite structure.Therefore, can form the film of further occlusion lithium.When forming the noncrystalline carbon film by this AIP method, in same chamber, if Sn and 4A, 5A, 6A family element are evaporated by vacuum vapour deposition or sputtering method, then can form the noncrystalline carbon film (negative electrode active material) of the carbide that contains Sn and 4A, 5A, 6A family element.In addition, when discharging by the AIP method, when implemented on appropriate hydrocarbon gas limits such as limit importing methane or ethene, by arc discharge, these appropriate hydrocarbon gas were decomposed and are deposited in the negative electrode collector surface as the amorphous carbon film, therefore, film forming speed are further improved.
Then,, an example of the manufacture method of the anode material for lithium-ion secondary battery 10 of the situation of using sputtering method and the situation of using the AIP method is described,, then be not limited to these materials so long as use the material of vapour deposition process with reference to Fig. 2,3.In addition, at this, the situation of using Sn (tin) and Zr (zirconium) is described.In addition, the formation of sputter equipment and AIP-sputter set composite is not limited to the formation shown in Fig. 2,3, can use known device.
For the situation of using sputtering method, as shown in Figure 2, carbon target 22, tin target 23, and the zirconium target 24 of φ 100mm * thickness 5mm at first are set in the chamber 21 of sputter equipment 20, and the Copper Foil 25 that will grow 50 * wide 50 * thickness 0.02mm according to subtend in carbon target 22, tin target 23, and the mode of zirconium target 24 be arranged on substrate platform 26.Then, be 1 * 10 according to the pressure in the chamber 21 -3The following mode of Pa vacuumizes, and makes in the chamber 21 to be in vacuum state., in chamber 21, import Ar gas, make the pressure in the chamber 21 become 0.26Pa thereafter, to carbon target 22, tin target 23, and zirconium target 24 apply DC (direct current) and produce plasma, sputtered carbon target 22, tin target 23, and zirconium target 24.Thus, film forming is dispersed with the film (negative electrode active material) of tin and zirconium carbide in amorphous carbon on Copper Foil 25.Thus, can make anode material for lithium-ion secondary battery.
For the situation of using the AIP method, as shown in Figure 3, at first in the chamber 31 of AIP-sputter set composite 30, graphite target 32, and tin target 33 and the zirconium target 34 of 6 inches * thickness of φ 6mm of φ 100mm * thickness 16mm are set, and the Copper Foil 35 that will grow 50 * wide 50 * thickness 0.02mm is arranged on substrate platform cylindraceous 36 surfaces of revolution.Then, be 1 * 10 according to the pressure in the chamber 31 -3The following mode of Pa vacuumizes, and makes in the chamber 31 to be in vacuum state.Thereafter, in chamber 31, import Ar gas, make the pressure in the chamber 31 become 0.26Pa, to graphite target 32, tin target 33, and zirconium target 34 apply DC (direct current), thereby make graphite target 32 produce arc discharge, make tin target 33 and zirconium target 34 produce glow discharge, graphite is evaporated by the heat of arc discharge, and tin and zirconium are evaporated by the sputter of argon.Thus, film forming is dispersed with the film (negative electrode active material) of tin and zirconium carbide in amorphous carbon on Copper Foil 35.Like this, can make anode material for lithium-ion secondary battery.
In addition, carry out above-mentioned each operation not being produced in the dysgenic scope when of the present invention at every turn, between above-mentioned each operation or front and back for example can comprise negative electrode collector matting, temperature and adjust operation etc., also can comprise other operations.
" lithium rechargeable battery "
Lithium rechargeable battery of the present invention is the battery of the anode material for lithium-ion secondary battery of the above-mentioned record of use.The negative material of the application of the invention can be made and has high charge/discharge capacity, cell excellent in cycle characteristics and the lithium rechargeable battery that can discharge and recharge at a high speed.
" form of lithium rechargeable battery "
As the form of lithium rechargeable battery, can enumerate cylinder type, Coin shape, substrate lift-launch film-type, angle type, sheet type etc., as long as can use negative material of the present invention, then can be variety of way.
The electrolyte that lithium rechargeable battery mainly moves by negative material, positive electrode, with the isolated material of these electrode materials insulation, electric charge between auxiliary electrode material, the battery case of accommodating these constitute.
Below, each formation is described.
＜negative material 〉
Negative material uses above-mentioned negative material of the present invention, and in addition, this negative material is made by the manufacture method of foregoing invention.
＜positive electrode 〉
There is no particular limitation for positive electrode, can use for example LiCoO of material known 2, LiNiO 2, LiMn 2O 4Deng the otide containing lighium thing.Manufacture method to positive electrode also is not particularly limited, can utilize known method, for example pulverous these positive electrodes are added adhesives and add electric conducting material, solvent etc. as required and carry out fully mixing after, be coated on the collector bodies such as aluminium foil, and carry out drying, extruding and make.
＜isolated material 〉
Isolated material is not particularly limited, can uses material known, for example polyolefin such as polyethylene, polypropylene is as the isolated material of the sheet material of the porous plastid of raw material or nonwoven fabrics etc.
＜electrolyte 〉
Electrolyte injects in the battery case and carries out airtight.This electrolyte can carry out moving of the lithium ion that generates because of the electrochemical reaction on negative material and positive electrode when discharging and recharging.
As the electrolyte solvent of electrolyte, can use the known non-proton property of solubilized lithium salts, the solvent of low-k.For example, can separately or mix a plurality of following solvents uses, described solvent is: ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, second eyeball, propionitrile, oxolane, gamma-butyrolacton, 2-methyltetrahydrofuran, 1,3-two oxa-s penta ring, 4-methyl isophthalic acid, 3-two oxa-s penta ring, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, Anaesthetie Ether, sulfolane, methyl sulfolane, nitromethane, N, dinethylformamide, dimethyl sulfoxide (DMSO) equal solvent.
Lithium salts as using as the electrolyte of electrolyte can use for example LiClO 4, LiAsF 6, LiPF 6, LiBF 4, LiB (C 6H 5) 4, LiCl, CH 3SO 3Li, CF 3SO 3Li etc., can use separately these salt or can be a plurality of mixing use.
＜battery case 〉
Battery case is accommodated above-mentioned negative material, positive electrode, isolated material, electrolyte etc.
In addition, under the situation of making lithium solid secondary cell, polymerization lithium secondary battery, by using anode material for lithium-ion secondary battery of the present invention simultaneously, can make secondary cell safe, high power capacity with known positive electrode, condensate electrolyte, solid electrolyte.
[embodiment]
Then, for anode material for lithium-ion secondary battery of the present invention and manufacture method and lithium rechargeable battery, the comparative example that satisfies the important document of the embodiment of important document of the present invention and discontented unabridged version invention is compared and be specifically described.
[first embodiment]
Make test portion by following method.
In the chamber in sputter equipment as shown in Figure 2, purity 99.99%), and zirconium target (high-purity chemical Co., Ltd. system: purity 99.2%) carbon target, tin target (high-purity chemical Co., Ltd. system: of φ 100mm * thickness 5mm is set, and the Copper Foil (nilaco of Co., Ltd. system) that will grow 50 * wide 50 * thickness 0.02mm according to subtend in carbon target, tin target, and the mode of zirconium target be arranged at the substrate platform, be 1 * 10 according to the pressure in the chamber -3The following mode of pa vacuumizes, and makes to be in vacuum state in the chamber., in chamber, import Ar gas, make the pressure in the chamber become 0.26Pa thereafter, to carbon target, tin target, and the zirconium target apply DC (direct current) and produce plasma, sputtered carbon target, tin target, and zirconium target.Thus, in amorphous carbon, be dispersed with the film of tin and zirconium carbide, thereby make anode material for lithium-ion secondary battery in film forming on the Copper Foil.
At this moment, put on carbon target, tin target, and the DC power of zirconium target by adjustment, the composition of control carbon, tin, zirconium is made the embodiment 1～4 shown in the table 1 and the negative material of comparative example 1～3,5.In addition, thickness all is set at 1 μ m.In addition, use adhesive that graphite is coated on the Copper Foil in the comparative example 4, and it is carried out drying, extruding and makes graphite cathode material.
In addition, observe the dispersity in the amorphous carbon of the embodiment 1 investigation negative material shown in the his-and-hers watches 1 by FIB-TEM.Consequently, the carbon when FIB-TEM observes exists mutually with amorphous, observes the structure of the zirconium carbide of the tin particle that is dispersed with 2～5nm size in amorphous carbon and 5～10nm size.
To the test portion of such manufacturing, carry out the charge-discharge characteristic evaluation by following method.
[charge-discharge characteristic evaluation]
The negative material that obtains of configuration and to the lithium metal of the utmost point as positive electrode, the isolated material of the porous plastid of clamping polypropylene system between two electrode materials.As electrolyte, use the 6 fluorinated phosphate lithium salts of 1mol/l are dissolved in the solution that the mixed organic solvents of ethylene carbonate and dimethyl carbonate forms with 1 pair 1 of volume ratio, make the evaluation electricity pool unit of two utmost point formula battery units.In addition, Fig. 4 represents the schematic diagram of the structure of the evaluation electricity pool unit that uses.
To this evaluation electricity pool unit, at room temperature, the speed of discharging and recharging is made as 0.2C and 10C two kinds, 1.2V carried out with discharging and recharging as 100 circulations under the 10C as a circulation when cut-ff voltage was made as 0.005V, discharge.And, try to achieve the first discharge capacity (initial stage discharge capacity) that discharges and recharges under speed 0.2C and the 10C and discharge and recharge the inferior capacity sustainment rate of the circulation of the 100th under the speed 10C.In addition, the capacity sustainment rate is tried to achieve by the formula of " inferior discharge capacity ÷ initial stage discharge capacity * 100 of the 100th circulation ", and the initial stage discharge capacity under the 10C is more than the 250mA/g, and the inferior capacity sustainment rate of the 100th circulation is being qualified more than 75%.At this, the C of unit that expression discharges and recharges speed is full of electricity from the state of having put electricity, and perhaps from being full of electricity to the time that has put electricity, 1C represents to be full of electricity with 1 hour, and 10C represents to be full of with 1/10 hour=6 minutes.
These results of table 1 expression.In addition, the content of each element in the table is tried to achieve by following Auger electron spectroscopy analysis (AES analysis).In addition, in table 1, the material of the formation of discontented unabridged version invention reaches the material that does not satisfy metewand and represents with underscore under numerical value.
(composition analysis)
Auger electron spectroscopy analysis (AES analysis) is implemented in the analysis of forming, and has obtained the concentration of element in the film.At this, AES analyzes and uses the system PHI650 of PerkinElmer society sweep type Auger electron spectrometer, and the zone of diameter 10 μ m is analyzed.Sneak into inevitably when in film, having the film forming below the 10at% from impurity such as the copper of substrate and oxygen, remove these, (atomic fraction of Sn)/(atomic fraction of atomic fraction+C of atomic fraction+Zr of Sn) formed as Sn in the film, equally, (atomic fraction of Zr)/(atomic fraction of atomic fraction+C of atomic fraction+Zr of Sn) and (atomic fraction of C)/(atomic fraction of atomic fraction+C of atomic fraction+Zr of Sn) are calculated as Zr composition in the film and C composition respectively.
[table 1]
Figure GSA00000138166100121
As shown in table 1, because embodiment 1～4 satisfies important document of the present invention,, show high initial stage discharge capacity and the inferior capacity sustainment rate of the 100th circulation so the comparative example 4 that graphite is coated on the Copper Foil is compared with using adhesive.
On the other hand, because in comparative example 1, Sn content is more, thus the capacity height at initial stage, but in cyclic test deterioration.In comparative example 2, because Zr content is too much, and the excessive formation of carbide, therefore, if improve the diffusion that discharges and recharges speed then hinder Li, than using adhesive that the initial stage discharge capacity that graphite is coated on the comparative example 4 on the Copper Foil is reduced.In comparative example 3, because Zr content is little, thus show high initial stage discharge capacity to discharge and recharge speed 0.2C, but when the speed that discharges and recharges formed 10C, electronic conductivity worsened, thereby initial capacity reduces.That is the material of comparative example 2,3, for not discharging and recharging at a high speed.In addition, because the Sn content of comparative example 5 is few,, do not increase the effect of charge/discharge capacity so the charge/discharge capacity at initial stage does not almost have difference with comparative example 4.
[second embodiment]
Identical with first embodiment, use sputter equipment to become membrane negative electrode material.But, the zirconium target is changed into other 4A, 5A, 6A family element target and implement film forming.The result is as shown in table 2.
[table 2]
Figure GSA00000138166100131
As shown in table 2, by adding 4A, 5A, 6A family element,, also can show and discharge and recharge the initial stage discharge capacity of speed 0.2C with degree even the speed of discharging and recharging is 10C.In addition, as can be known, by adding Sn, it is higher that the initial stage discharge capacity is compared with comparative example 4, and by Sn is adjusted within the scope of the invention, cycle characteristics is also good.
[the 3rd embodiment]
In the 3rd embodiment, as film build method,, use sputtering method film forming Sn and Cr simultaneously by using AIP method film forming amorphous carbon, make the lithium ion battery negative material thus.
In the chamber of as shown in Figure 3 AIP-sputter equipment, purity 99.99%) and chromium target (high-purity chemical Co., Ltd. system: purity 99.9%) graphite target, and the tin target of 6 inches * thickness of φ 6mm (the high-purity chemical Co., Ltd. system: of φ 100mm * thickness 16mm are set, and the Copper Foil (nilaco of Co., Ltd. system) that will grow 50 * wide 50 * thickness 0.02mm is arranged on the substrate platform cylindraceous surface of revolution, is 1 * 10 according to the pressure in the chamber -3The following mode of Pa vacuumizes, and makes to be in vacuum state in the chamber.Thereafter, in chamber, import Ar gas, make the pressure in the chamber become 0.26Pa, to graphite target, tin target, and the chromium target apply DC (direct current), make graphite target produce arc discharge, make tin target and chromium target produce glow discharge, make the thermal evaporation of graphite, and make tin and chromium sputter vaporization by argon by arc discharge.Thus, in amorphous carbon, be dispersed with the film (negative electrode active material) of tin and chromium carbide, make anode material for lithium-ion secondary battery in film forming on the Copper Foil.The arc discharge electric current of this moment is that 60A, sputtering power are 500W, and the bias voltage that puts on substrate is 10V, carries out 1 hour film forming.
Dispersity to tin in the amorphous carbon of this negative material and chromium, investigate by the FIB-TEM observation, carbon is for containing the disorderly structure of the graphite of layer structure in the noncrystalline structure, carbon mutually in, the structure of the chromium carbide particle of the tin particle that is dispersed with particle diameter 5～10nm size and 10～15nm size is observed.In addition, observe with the SEM pair cross-section, the thickness of negative material is 5 μ m.In addition, Sn is identical with embodiment 2 with the analysis that Cr forms, and implements Auger electron spectroscopy analysis (AES analysis), and obtaining Sn is that 3at%, Cr are 5at%.
To the test portion of such manufacturing, by the method identical, carry out the charge-discharge characteristic evaluation, the capacity sustainment rate when trying to achieve the mensuration of the initial stage discharge capacity that discharges and recharges under speed 0.2C and the 10C and discharging and recharging 500 cycle charge-discharges under the speed 10C with second embodiment.Its result, initial stage discharge capacity are 415mAh/g when 0.2C, are 410mAh/g when 10C, and the capacity sustainment rate is 83%.Like this, for making the amorphous carbon film forming with the AIP method, and make Sn and Cr film forming and the negative material that obtains is compared with a comparative example of film forming graphite 4 simultaneously with sputtering method, show high initial stage discharge capacity, the capacity sustainment rate also shows more than 75%.
From above result as can be known, according to anode material for lithium-ion secondary battery of the present invention, can obtain having both sufficient charge/discharge capacity, good cycle characteristics and the lithium rechargeable battery that can discharge and recharge at a high speed.
More than execution mode, the embodiment of the best of the present invention is illustrated, but the present invention is not limited to above-mentioned execution mode, embodiment, can broadly change in being suitable for the scope of aim of the present invention and change, these all are included in the technical scope of the present invention.

Claims (4)

1. anode material for lithium-ion secondary battery, it is used for lithium rechargeable battery, it is characterized in that,
Described anode material for lithium-ion secondary battery forms negative electrode active material and forms on negative electrode collector, described negative electrode active material is to disperse the Sn of 1～40at% and at least a metal that is selected from 4A, 5A, the 6A family element of 3～20at% to form in amorphous carbon.
2. the manufacture method of anode material for lithium-ion secondary battery according to claim 1 is characterized in that,
By vapour deposition process, negative electrode active material is formed on the negative electrode collector, described negative electrode active material is to disperse the Sn of 1～40at% and at least a metal that is selected from 4A, 5A, the 6A family element of 3～20at% to form in amorphous carbon.
3. the manufacture method of anode material for lithium-ion secondary battery according to claim 2 is characterized in that,
Use graphite target, form the amorphous carbon of described negative electrode active material by the arc ion plating method.
4. a lithium rechargeable battery is characterized in that,
Possesses the described anode material for lithium-ion secondary battery of claim 1.
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