CN101908617A - 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 PDFInfo
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- CN101908617A CN101908617A CN2010101963569A CN201010196356A CN101908617A CN 101908617 A CN101908617 A CN 101908617A CN 2010101963569 A CN2010101963569 A CN 2010101963569A CN 201010196356 A CN201010196356 A CN 201010196356A CN 101908617 A CN101908617 A CN 101908617A
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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
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- 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
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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
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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
- H01M4/58—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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention provides and a kind ofly have both high charge/discharge capacity, good cycle characteristics and discharge and recharge the anode material for lithium-ion secondary battery of speed fast and manufacture method and the lithium rechargeable battery that uses anode material for lithium-ion secondary battery.A kind of anode material for lithium-ion secondary battery (10) that is used for lithium rechargeable battery, it is characterized in that, anode material for lithium-ion secondary battery (10) is upward to form the material that Sn and Ag are scattered in the negative electrode active material (2) that forms in the amorphous carbon at negative electrode collector (1), the content of the amorphous carbon of negative electrode active material (2) is more than 50at%, and the ratio (Sn/Ag) of Sn content and Ag content is 0.5～4.
Description
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
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 them constitute.And anode material for lithium-ion secondary battery is that coating negative electrode active material material forms on the current-collecting member that is made of Copper Foil or copper alloy foil.As negative electrode active material, generally using graphite is material with carbon element.
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 energy density (charge/discharge capacity), and therefore, beginning is extensive use of as the power supply of above-mentioned portable equipment.
In addition, along with the raising of environmental consciousness, wish that automobile from present use fossil fuel is to CO
2The electric automobile that discharge rate is few, hybrid vehicle change, as the battery that is equipped on these formations, to the expectation raising of lithium rechargeable battery.
The characteristic of pursuing as the battery that is equipped on electric automobile and hybrid vehicle, can enumerate except that (the endurance distance increase of each charging of energy density height, need the number of times of charging to reduce), outside the cycle characteristics good (extending the life of a cell), the speed that discharges and recharges is at a high speed.At this, so-called cycle characteristics is meant, even the circulation that repeats to discharge and recharge can not make negative electrode active material deterioration (peel off, come off etc.), the character that charge/discharge capacity does not reduce yet.
Wherein, the speed of discharging and recharging is the special performance of pursuing of battery that is equipped on automobile, if charging rate is fast, even then under the situation that the energy that is stored in battery is used up, also can return the state of full charging with the short charging interval.In addition, under the fast situation of charging rate, the energy that loses as heat when using regenerative braking reduces, and therefore, can utilize energy effectively again, also is related to the increase of endurance distance.On the other hand, the fast velocity of discharge is related to good acceleration performance.
Usually, in being equipped on the battery of electric automobile, target be can be minimum discharging and recharging for the electric current of 10C speed (10C speed for can with the electric current that completely discharged and recharged in 6 minutes) degree.
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 on collector body 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, there is the such problem of the bigger reduction of charge/discharge capacity in the result.
As the scheme that addresses this problem, in order to relax the change in volume of negative electrode active material, 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 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 finishes in view of above-mentioned problem, a kind of anode material for lithium-ion secondary battery and manufacture method thereof that has both high charge/discharge capacity, good cycle characteristics and the fast speed that discharges and recharges is provided, 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 is for forming the material that Sn and Ag are scattered in the negative electrode active material that forms in the amorphous carbon on negative electrode collector, the content of the amorphous carbon of described negative electrode active material is more than 50at%, and the ratio (Sn/Ag) of Sn content and Ag content is 0.5～4.
According to such formation, Sn and Ag do not carry out alloying with carbon and are dispersed in the amorphous carbon with nano-particles size.And, Sn occlusion Li and cause big change in volume, but owing to be dispersed in the noncrystalline carbon film, so by the sp in the crystal structure of amorphous carbon
3In conjunction with, relax change in volume.In addition, the content of amorphous carbon is in prescribed limit, so the change in volume of Sn is further relaxed.Therefore, charge/discharge capacity (specific mass capacity or specific volume capacity) improves, simultaneously, negative electrode active material from the peeling off of collector body, break, micronizing (cycle characteristics is good) is suppressed.And, be dispersed between Ag in the amorphous carbon and the Li and do not form intermetallic compound, but owing to have the phase of a large amount of Li of solid solution, therefore, effect with the diffusion velocity that improves the Li ion in the negative electrode active material, simultaneously, owing to be metallic element, therefore, the effect that has the electronic conductivity that improves negative electrode active material.In addition and since with the content of the Ag of the ratio regulation of the content of Sn in prescribed limit, so the diffusion velocity of Li ion and electronic conductivity further improve.Therefore, have high charge/discharge capacity, good cycle characteristics, simultaneously, it discharges and recharges speed and improves.
The manufacture method of anode material for lithium-ion secondary battery of the present invention is the manufacture method of described anode material for lithium-ion secondary battery, it is characterized in that, forms described negative electrode active material by vapour deposition process on negative electrode collector.
According to such manufacture method, by using vapour deposition process, Sn and Ag effectively disperse in amorphous carbon.In addition, the control by film thickness of the control of the composition of amorphous carbon, Sn and Ag and negative electrode active material becomes easy.
In addition, the invention provides a kind of manufacture method of anode material for lithium-ion secondary battery, it is characterized in that, use graphite target, form the amorphous carbon of described negative electrode active material by the arc ion plating method.
According to such manufacture method, film forming speed is fast, therefore, can realize thick filmization, in addition, and by forming the many films of graphite-structure, occlusion lithium easily.
Lithium rechargeable battery of the present invention is characterised in that, uses described anode material for lithium-ion secondary battery.
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 and good cycle characteristics and the good lithium rechargeable battery of high speed charge-discharge characteristic.
According to anode material for lithium-ion secondary battery of the present invention, have the diffusion velocity of the Li ion in the negative electrode active material of high charge/discharge capacity and good cycle characteristics and the electronic conductivity of negative electrode active material by raising, can obtain the also excellent anode material for lithium-ion secondary battery of the speed of discharging and recharging.
According to the manufacture method of anode material for lithium-ion secondary battery of the present invention, can make the anode material for lithium-ion secondary battery that has both high charge/discharge capacity, good cycle characteristics and the fast speed that discharges and recharges.In addition, by using vapour deposition process, can on negative electrode collector, form negative electrode active material easily and easily.In addition, by using the arc ion plating method of graphite target, charge/discharge capacity is further improved.
Lithium rechargeable battery of the present invention not only has high charge/discharge capacity, good cycle characteristics, and can bring into play high capacity when discharging and recharging at a high speed.
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;
Fig. 5 is a curve chart of representing the relation of the containing ratio of the amorphous carbon in the negative electrode active material in an embodiment and the capacity sustainment rate after carrying out 100 circulations under the 10C speed;
Fig. 6 is relation, and the curve chart of representing between the ratio (10C/1C) of the relative 1C initial capacity with the 10C initial capacity of Sn/Ag in the negative electrode active material in an embodiment of the relation of Sn/Ag and 1C initial capacity.
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 and is formed on negative electrode active material 2 on the negative electrode collector 1.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, produce the expansion of following negative electrode active material 2, together the fold of generation stretching (plastic deformation) 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 1～30 μ m.
＜negative electrode active material 〉
Negative electrode active material 2 is for to be dispersed with Sn and Ag in amorphous carbon, the content of amorphous carbon is more than the 50at%, and the ratio (Sn/Ag) of Sn content and Ag content is 0.5～4 material.And the impurity from negative electrode collector of sneaking into inevitably when having film forming in negative electrode active material 2 (copper and oxygen etc.), but is in the present invention removed this impurity and is calculated C, Ag, Sn content.Therefore, negative electrode active material 2 is made of C, Sn and Ag, and the content of C is more than the 50at%, the content of Sn and the content of Ag add up to not enough 50at%.
[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
3Play the effect of the change in volume that is scattered in the Sn in the amorphous carbon when suppressing to discharge and recharge in conjunction with (carbon matrix).In addition, increase this point from charge/discharge capacity, amorphous carbon preferably has the structure of the lithium of occlusion graphite structure etc.
The content of the amorphous carbon in the negative electrode active material 2 is more than the 50at%.By in amorphous carbon, disperseing Sn and Ag, can realize the raising of charge/discharge capacity, cycle characteristics and high speed charge-discharge characteristic, particularly be set in the above-mentioned scope by content with amorphous carbon, even after discharging and recharging repeatedly, owing to can relax the change in volume of Sn by the carbon matrix, so also can obtain good cycle characteristics.Amorphous carbon contain quantity not sufficient 50at% the time, can not the change in volume of Sn be relaxed by the carbon matrix, cycle characteristics worsens.Be preferably more than the 55at%, more preferably more than the 60at%.
[Sn and Ag]
Since Sn and Ag be can with lithium alloyage and low-melting metal, so be scattered in the amorphous carbon with the high non-alloying of carbon of fusing point.And, the content of Sn and the content of Ag add up to not enough 50at%, it is set at 0.5～4 than being set at (Sn/Ag).
By being dispersed in the amorphous carbon that accounts in the negative electrode active material 2 more than the 50at%, Sn and Ag (be separated into the nanometer crystal druse shape), and Sn/Ag is set at 0.5～4, compare the negative material 10 that can form charge/discharge capacity and cell excellent in cycle characteristics and can discharge and recharge at a high speed with present negative material.
By in the amorphous carbon of negative electrode active material 2, disperseing Sn and Ag, can realize the raising of charge/discharge capacity and high speed charge-discharge characteristic.Particularly, can further improve charge/discharge capacity and high speed charge-discharge characteristic by Sn/Ag is set at 0.5～4.At this, Sn improves charge/discharge capacity by occlusion Li.And Ag can improve the high speed charge-discharge characteristic by the diffusion velocity of raising Li ion and the electronic conductivity of negative electrode active material 2.
Sn/Ag in negative electrode active material 2 surpasses at 4 o'clock, and with respect to the Sn that takes on the Li occlusion, the amount of Ag of conduction of taking on the diffusion of Li ion and electronics is few, and therefore, the effect that improves the speed that discharges and recharges reduces.In addition, when Sn/Ag less than 0.5, the ratio of the Sn that takes on the Li occlusion in the negative electrode active material 2 reduces, so charge/discharge capacity reduces.
At this, be scattered in Sn in the amorphous carbon and the particle diameter of Ag and be preferably 0.5～100nm.By the particle size dispersion that makes Sn and Ag is the nanometer crystal druse shape of 0.5～100nm, and Sn when discharging and recharging and the change in volume of Ag are further relaxed, and can realize the raising of charge/discharge capacity and high speed charge-discharge characteristic.
The control of the particle diameter of Sn and Ag is undertaken by the composition of amorphous carbon and metal (Sn and Ag) in the control negative electrode active material 2.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 Sn and Ag 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 of the composition of negative electrode active material 2 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, Sn and Ag will be disperseed in the amorphous carbon that be characterized as more than accounting for 50at%, and the ratio of Sn/Ag is 0.5～4 negative electrode active material 2, is 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, Sn and Ag will be disperseed in the amorphous carbon that be characterized as more than accounting for 50at%, and the ratio of Sn/Ag is 0.5～4 negative electrode active material 2, is 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 and grinding etc. by negative electrode collector.
＜negative electrode active material forms operation 〉
Negative electrode active material forms operation for to be scattered in Sn and Ag in the amorphous carbon that accounts for more than the 50at% by vapour deposition process, simultaneously, make negative electrode active material 2, be formed on the operation on the negative electrode collector 1 by the dispersion formation of Sn in above-mentioned amorphous carbon and Ag.
By using vapour deposition process, Sn and Ag are disperseed with nanometer crystal druse shape ground in the amorphous carbon more than accounting for 50at%, simultaneously, can on negative electrode collector 1, form negative electrode active material 2.In addition, the composition of amorphous carbon and metal (Sn and Ag) freely can be controlled in the wide scope, simultaneously, also can easily control tunicle (negative electrode active material 2) thickness, negative electrode active material 2 is formed on the negative electrode collector 1 easily and easily.The thickness of tunicle is preferably 0.1～100 μ m.
In addition, in manufacture method of the present invention, owing to use vapour deposition process, therefore, Sn and Ag are dispersed in the film (negative electrode active material 2) that forms in the amorphous carbon are formed on by evaporation and obtain negative material 10 on the negative electrode collector 1 by making.Therefore, can omit in the present manufacture method graphite matter carbon dust is 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 more film of occlusion lithium.In the noncrystalline carbon film that forms this AIP method, in same chamber,, then can form the noncrystalline carbon film (negative electrode active material 2) that contains Sn and Ag if Sn and Ag are evaporated by vacuum vapour deposition or sputtering method.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, the formation of sputter equipment 20 and AIP-sputter set composite 30 is not limited to shown in Fig. 2,3, can use known device.
For the situation of using sputtering method, as shown in Figure 2, at first in the chamber 21 of sputter equipment 20, the carbon target 23 of φ 100mm * thickness 5mm and tin target 22, and silver-colored target 24 are set, and substrate (Copper Foil) 25 that will grow 50 * wide 50 * thickness 0.02mm according to subtend in carbon target 23, tin target 22, and the mode of silver-colored target 24 be provided with.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., to chamber 21 in import Ar gas, make the pressure in the chamber 21 become 0.26Pa, each target is applied DC (direct current) and produces plasma, sputtered carbon target 23, tin target 22, and silver-colored target 24 thereafter.Thus, film forming is dispersed with the film (negative electrode active material) of tin and silver in amorphous carbon on as substrate (Copper Foil) 25 of negative electrode collector.Thus, can make anode material for lithium-ion secondary battery.
For the situation of using the AIP method, as shown in Figure 3, graphite target 32, and silver-colored target 33 and the tin target 34 of 6 inches * thickness of φ 6mm of φ 100mm * thickness 16mm at first 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 in the chamber 31 of AIP-sputter set composite 30.Then, be that the following mode of 1 * 10-3Pa vacuumizes according to the pressure in the chamber 31, make 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 34, and silver-colored target 33 applies DC (direct current) and make graphite target 32 produce arc discharges, make silver-colored target 33 and tin target 34 produce glow discharge, graphite is evaporated by the heat of arc discharge, and tin and silver are evaporated by the sputter of argon.Thus, film forming is dispersed with the film (negative electrode active material) of tin and silver in amorphous carbon on as the Copper Foil 35 of negative electrode collector.Thus, 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 also 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, good cycle characteristics, and the good lithium rechargeable battery of high speed charge-discharge characteristic.
" form of lithium rechargeable battery "
As the form of lithium rechargeable battery, for example 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, to 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 is specifically described.
[first embodiment]
Carbon target, tin target and the silver-colored target (Furuchi KCC) of φ 100mm * thickness 5mm are set in the chamber of as shown in Figure 2 sputter equipment.In addition, the Copper Foil (Furuchi KCC) that will grow 50 * wide 50 * thickness 0.02mm according to subtend in carbon target, tin target, and the mode of silver-colored target be provided with.Then, 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., to chamber in import Ar gas, make the pressure in the chamber become 0.26Pa, each target is applied DC (direct current) and produces plasma, sputtered carbon target, tin target, and silver-colored target thereafter.Put on the electric current of each target by adjustment, go up film forming at Copper Foil (negative electrode collector) and in amorphous carbon, disperses tin and the silver-colored film (negative electrode active material) that forms, thereby, anode material for lithium-ion secondary battery can be made.
Ag, the Sn of film (negative electrode active material) and C content are calculated by Auger electron spectroscopy analysis (AES analysis).At this, AES analyzes and uses the system PH1650 of Perkinelmer society sweep type Auger electron spectrometer, and the zone of diameter 10 μ m is analyzed.Sneak into inevitably when in film (negative electrode active material), having the film forming below the 10at% from impurity such as the copper of Copper Foil and oxygen, they are removed, can calculate Ag, Sn, C content in the film (negative electrode active material).
Negative material (test portion No.1～8) to such manufacturing carries 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 batteries.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, be made as the discharge and recharge test of 1.0V when carrying out being made as 0.1V, discharge when cut-ff voltage charged as a circulation.Discharging and recharging test is undertaken by constant current.
Current settings was 1C speed, the initial stage discharge capacity when reaching 10C speed when mensuration discharged and recharged.In addition, under 10C speed, carry out the test that discharges and recharges of 100 circulations, and measure the capacity sustainment rate of this moment.At this, the capacity sustainment rate is calculated by " discharge capacity ÷ initial stage discharge capacity * 100 after 100 circulations ".
Initial stage discharge capacity (initial capacity) under the 1C speed is under the situation that surpasses 560mAh/g (present graphite cathode material theoretical capacity about 1.5 times), and charge/discharge capacity is good.
In addition, surpassing under 80% the situation of initial stage discharge capacity under the 1C speed high speed charge-discharge characteristic good (that is, discharge and recharge speed fast) in the initial stage discharge capacity (initial capacity) under the 10C speed.
And then to be that material more than 80% is set at cycle characteristics good with the capacity sustainment rate after the test of discharging and recharging of 100 under 10C speed circulation.
These results are as shown in table 1.In addition, Fig. 5 represents the relation that discharges and recharges the capacity sustainment rate after the test of 100 circulations under the content of the amorphous carbon in the film and the 10C speed.In addition, Fig. 6 represents the relation between the ratio (10C/1C) of the relative 1C initial capacity with the 10C initial capacity of the Sn/Ag in the film, and the relation between Sn/Ag and the 1C initial capacity.
[table 1]
(notes) 10C/1C:10C initial capacity is with respect to the ratio of 1C initial capacity
As shown in table 1, owing to satisfy important document of the present invention, therefore can bring into play sufficient charge-discharge characteristic (charge/discharge capacity, high speed charge-discharge characteristic and cycle characteristics) as test portion No.1～4 of embodiment.
On the other hand, the comparative example (test portion No.5) of the important document of the discontented unabridged version invention of the C content in the film can not be given full play to cycle characteristics.In addition, do not comprise the comparative example (test portion No.7) of Ag in the comparative example (test portion No.6) of the important document of the discontented unabridged version invention of the Sn/Ag in film, the film, can not bring into play sufficient high speed charge-discharge characteristic.In addition, the comparative example (test portion No.8) that does not comprise Sn in film can not be brought into play sufficient charge/discharge capacity.
In addition, in test portion No.1～4 as embodiment, when observing with FIB-TEM, being scattered in Sn in the amorphous carbon of film (negative electrode active material) and the particle diameter of Ag is 2～5nm, and when observing with SEM, the thickness of film is 0.45～0.55 μ m.
[second embodiment]
In a second embodiment,,, use sputtering method film forming Sn and Ag simultaneously, make the lithium ion battery negative material thus by using AIP method film forming amorphous carbon as film build method.
In the chamber of as shown in Figure 3 AIP-sputter set composite, the graphite target of φ 100mm * thickness 16mm, tin target and the silver-colored target (Furuchi KCC) of 6 inches * thickness of φ 6mm are set, and the Copper Foil (Furuchi KCC) 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 silver-colored target apply DC (direct current), thereby make graphite target produce arc discharge, make tin target and silver-colored target produce glow discharge, graphite is evaporated by the heat of arc discharge, and tin and silver are evaporated by the sputter of argon.Thus, go up the film (negative electrode active material) that film forming disperses tin and silver to form in amorphous carbon, made anode material for lithium-ion secondary battery at Copper Foil (negative electrode collector).The arc discharge electric current of this moment is that 60A, sputtering power are 500W, and the bias voltage that puts on Copper Foil (substrate) is 0V, carries out 1 hour film forming.
Dispersity to tin in the amorphous carbon in this negative material and silver, investigate by the FIB-TEM observation, carbon is for containing the disorderly structure of the graphite of layer structure in noncrystalline structure, carbon mutually in, the tin particle that is dispersed with particle diameter 5～10nm and the structure of silver particles are observed.In addition, observe with the SEM pair cross-section, the thickness of film (negative electrode active material) is 5 μ m.In addition, the analysis that C, Sn and Ag form is identical with embodiment 1, implements Auger electron spectroscopy analysis (AES analysis), and obtaining C is that 88at%, Sn are that 4at%, Ag are 8at%.
Test portion to such manufacturing, by the method identical with first embodiment, carry out the charge-discharge characteristic evaluation, its result, initial stage discharge capacity under 1C speed is 580mAh/g, the initial stage discharge capacity of situation about discharging and recharging under 10C speed is 530mAh/g, and the capacity sustainment rate after 100 circulations under the 10C speed is 96%.Like this, for making the amorphous carbon film forming, and make Sn and Ag film forming and the negative material that obtains shows good charge-discharge characteristic (charge/discharge capacity, high speed charge-discharge characteristic and cycle characteristics) simultaneously with sputtering method with the AIP method.
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 of high speed charge-discharge characteristic.
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 disperses Sn and Ag to form in amorphous carbon,
In the described negative electrode active material, the content of amorphous carbon is more than 50at%, and the ratio Sn/Ag of Sn content and Ag content is 0.5～4.
2. the manufacture method of anode material for lithium-ion secondary battery according to claim 1 is characterized in that,
By vapour deposition process, described negative electrode active material is formed on the negative electrode collector.
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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| Application Number | Priority Date | Filing Date | Title |
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| JP2009136724A JP5351618B2 (en) | 2009-06-05 | 2009-06-05 | Negative electrode material for lithium ion secondary battery, manufacturing method thereof, and lithium ion secondary battery |
| JP2009-136724 | 2009-06-05 |
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| CN101908617A true CN101908617A (en) | 2010-12-08 |
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| CN2010101963569A Pending CN101908617A (en) | 2009-06-05 | 2010-06-03 | Anode material for lithium-ion secondary battery and manufacture method thereof and lithium rechargeable battery |
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| JP (1) | JP5351618B2 (en) |
| KR (1) | KR101201126B1 (en) |
| CN (1) | CN101908617A (en) |
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| CN105977541A (en) * | 2016-06-28 | 2016-09-28 | 盈天科技（深圳）有限公司 | Production apparatus of lithium ion battery |
| CN106985683A (en) * | 2016-01-20 | 2017-07-28 | 福特全球技术公司 | Charging strategy for mitigating the lithium plating in electrified Vehicular battery |
| CN109309194A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | It is modified without cathode of lithium, preparation method and contains its lithium ion battery |
| CN109873113A (en) * | 2017-12-04 | 2019-06-11 | 钰邦科技股份有限公司 | Lithium battery structure and its negative electrodes for lithium batteries foil |
| CN115172666A (en) * | 2022-07-28 | 2022-10-11 | 华中科技大学 | Double-layer composite graphite cathode and preparation method thereof |
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| JP6303710B2 (en) * | 2014-03-28 | 2018-04-04 | 三菱マテリアル株式会社 | Method for producing negative electrode active material for lithium ion secondary battery |
| JP7134624B2 (en) * | 2016-12-15 | 2022-09-12 | ストアドット リミテッド | Electric vehicles with adaptable fast charging utilizing supercapacitor emulating batteries |
| JP2019096610A (en) | 2017-11-21 | 2019-06-20 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | All-solid type secondary battery and charging method thereof |
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| Publication number | Publication date |
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| JP5351618B2 (en) | 2013-11-27 |
| KR20100131368A (en) | 2010-12-15 |
| TWI416783B (en) | 2013-11-21 |
| KR101201126B1 (en) | 2012-11-13 |
| TW201110446A (en) | 2011-03-16 |
| JP2010282901A (en) | 2010-12-16 |
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