CN1111074A - Cell electrode, secondary cell using the cell electrode, and method for manufacturing the cell electrode - Google Patents
Cell electrode, secondary cell using the cell electrode, and method for manufacturing the cell electrode Download PDFInfo
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- CN1111074A CN1111074A CN94190416A CN94190416A CN1111074A CN 1111074 A CN1111074 A CN 1111074A CN 94190416 A CN94190416 A CN 94190416A CN 94190416 A CN94190416 A CN 94190416A CN 1111074 A CN1111074 A CN 1111074A
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Abstract
The present invention relates to an electrode for batteries comprising carbon fibers having a crystallite thickness of not less than 1.3 nm and not more than 1.7 nm according to X-ray diffraction method. The present invention also relates to a process for producing an electrode for batteries employing carbon fibers which is burned at a temperature between 900 DEG C and 1,330 DEG C. The present invention enabled to provide a secondary battery having the characteristics of the carbon fiber and a high discharging capacitance.
Description
Technical field
The present invention relates to the secondary cell that can discharge and recharge of electrode for cell and this electrode for cell of use.
Background technology
In recent years, along with popularizing of portable electronics such as gamma camera and notebook PC, the demand of the secondary cell of miniaturized high capacity is increased greatly.Used secondary cell nearly all is the nickel-cadmium cell that adopts alkaline electrolyte now, and when cell voltage hanged down to about 1.2V, energy density just was difficult to improve.Therefore, the someone has carried out with the research of the lithium metal in the base metal as the high-energy secondary cell of negative pole.
Yet, the lithium metal is used for the secondary cell of negative pole, owing to discharge and recharge operation repeatedly, lithium is grown to dendroid (dendrite), exists to cause short circuit and danger on fire.And, owing to use highly active lithium metal, in fact make dangerous the increase, a lot of problems are arranged when using as civil goods.In recent years, for solving this safety issue and having the distinctive high-octane battery of lithium battery, proposed to adopt the scheme of the lithium rechargeable battery of various carbon bodies.This method has been utilized such principle, that is since when charging lithium ion be doped in the carbon body, become the current potential identical with lithium metal, therefore can replace lithium metal and be used for negative pole.And during discharge, the lithium ion of doping takes off from negative pole and mixes, and becomes the matrix carbon body again.Like this, when the carbon body of the lithium ion that mixed is used as negative pole, owing to both do not generate dendritic problem, also do not have lithium metal, therefore have the characteristics of excellent safety, at present, these research and development are very active.
As above-mentioned employing utilize the secondary cell that the electrode of doped lithium ion is made in carbon body, spy to open clear 62-90863 communique, spy to open clear 62-122066 communique etc. all be known.The general choice of powder shape of this carbon body for the ease of electrode moulding, also must be used the polymer adhesive of polytetrafluoroethylene or polyvinylidene fluoride etc.Yet,,, just can perhaps also can only make electrode without adhesive with a little binder if use the carbon fiber or the carbon fiber structure of non-powder as carbon body.Have, from for electrolytical chemical stability, for problems such as the structural stability that is caused volumetric expansion by doping, repeated charge characteristics, carbon fiber or carbon fiber structure also are good again.As the secondary cell that adopts kind electrode, the spy opens clear 60-54181 communique, spy, and to open clear 62-103991 communique etc. be known.
On the other hand, for being mingled with in carbon body (or mix) from just having begun one's study a long time ago, and accumulated a large amount of experiences, all the time, think that the carbon body that can mix is only limited to the carbon body of high graphitization degree (crystallization degree).But, in recent years, distinguished and can in the such low-crystalline carbon body of organic substance sintered body, mix, the care of this carbon body is improved just day by day.
Yet, also have a lot of doubtful points about the mechanism of in carbon body, mixing at present, do not establish as yet and explore the guilding principle of secondary cell, Yi Bian Yi Bian still be in the tentative wrong stage of developing carbon body that runs into repeatedly with high-performance carbon element body.Now, probing direction as high-performance carbon element body, existing is target direction with the amorphism carbon body, also having with the crystallinity carbon body is target direction, but with regard to relevant prior art, the charge/discharge capacity of carbon body is still big inadequately, therefore, also exist with these carbon bodies as the low problem of the battery capacity of active electrode.
The objective of the invention is to eliminate the shortcoming of said prior art, provide to have the advantage of making electrode with carbon fiber, and the good electrode for cell of charge/discharge capacity, and the secondary cell that uses kind electrode.
Implement optimum implementation of the present invention
The present invention has following formation in order to solve above-mentioned problem, that is, the present invention relates to adopt the crystallization thickness Lc that is measured by X-ray diffraction is 13～17
The electrode for cell that constitutes of carbon fiber, the secondary cell that uses kind electrode, and the manufacture method of electrode for cell.
Herein, crystallization thickness Lc is from the value of the half-amplitude at the indices of crystallographic plane (002) peak that is recorded by X-ray diffraction, calculates with following Scherrer formula.
Lc（002）＝Kλ/β
0cosθ
B（1）
Lc(002): micro-crystallization is perpendicular to the average thickness on (002) face direction; K:1.0; λ: the wavelength of X ray (during CuK α, being 1/54), β
0=(β
2 E-β
2 1)
, β
E: apparent half-amplitude (measured value), β
1: correction value, θ
B: Bragg angle.
Have no particular limits as carbon fiber used among the present invention, but the fibrous organic substance burned material that obtains with the fibrous organic substance of roasting is for well.Usually, the degree of crystallinity of so-called carbon fiber improves along with the increase of crystallization thickness Lc, and Lc is more little, and then degree of crystallinity is low more.The degree of crystallinity height of the carbon body then ionic mobility in the carbon body is low, therefore the problem that exists discharge capacity to reduce.Otherwise degree of crystallinity is crossed to hang down and is then made carbon body be difficult to be used as electrode owing to charing is insufficient.Therefore, use the crystallization thickness Lc that records by X-ray diffraction 13 among the present invention
More than, 17
Following carbon fiber.
And usually, degree of orientation P is the index of the degree of orientation axial with respect to carbon fiber of the carbon element aspect in the expression carbon fiber, and it can be measured by following method.
The carbon fiber axle is vertically placed on the fiber samples platform,, then in horizontal plane, the strong diffracted ray of (002) near the angle of diffraction 2 θ=26 °, occurs from right angle orientation irradiation X ray (Cu, K α).Then, in plane perpendicular to incident X-rays, Yi Bian make carbon fiber rotation, on one side in horizontal plane near the position the angle of diffraction 2 θ=26 ° the mensuration diffracted intensity to anglec of rotation dependence.The half-amplitude that to be obtained by the dependence of angle of this intensity is as angle H, and degree of orientation P is calculated by following formula.
P＝｛（180-H）/180｝×100（%） （2）
Carbon fiber generally all has orientation, and its expression carbon element aspect is arranged on certain orientation.Under the occasion of utilizing carbon fiber as active electrode material, orientation is too high, then causes on the structure anisotropy strong, because that directivity and easily causing is mixed is different, therefore, the tendency that the capacity of existing can not increase.Therefore, adopt degree of orientation P more than 70, the carbon fiber below 85 is better.
And the electricalresistivity of carbon fiber with regard to specific insulation, is the resistivity on the fibre length direction, can measure by following method.
By the sample of choosing suitable length in the carbon fiber bundle, being fixed on the insulation board by the phase mutual edge distance is on the copper electrode that is provided with of 500mm, and adds suitable load at an end of sample, makes sample be in unbending state.Read interelectrode resistance value R by resistance measurer
b(Ω), with L(cm) the expression interelectrode distance, with m(g) the expression sample mass, with 1(cm) expression length, and with A(g/cm
3) expression density, then electricalresistivity (Ω cm) can be calculated by following formula.
ρ＝（R
b/L）×｛m/（1×A）｝ （3）
Usually, carbon fiber has been well-known as the good conductor of electricity, and its resistivity has very big variation according to the difference of manufacture method etc.Utilizing under the situation of the big carbon fiber of resistivity as active electrode, becoming big, therefore existing the tendency that capacity can not improve owing to the resistance of electrode makes potential drop.On the other hand, the too small degree of crystallinity that then exists of resistivity improves, and the ion mobilance in the carbon body reduces, thus the tendency that causes capacity to reduce.Therefore, resistivity is 1.0 * 10
-3More than the Ω cm, 4.0 * 10
-3Ω cm is better following, preferably uses 1.0 * 10
-3More than the Ω cm, 2.5 * 10
-3The carbon fiber that Ω cm is following.
Have no particular limits as carbon fiber of the present invention, can use general organic substance burned material.Specifically, the pitch-based carbon fiber that can enumerate the PAN based carbon fiber that makes by polyacrylonitrile (PAN), make by the pitch of coal or oil etc., the cellulose family carbon fiber that makes by cellulose, gas-phase growth of carbon fibre of making by the gas of low-molecular-weight organic matter etc., in addition, also can use roastings such as polyvinyl alcohol, lignin, polyvinyl chloride, polyamide, polyimides, phenolic resins, furfuryl alcohols and the carbon fiber that obtains.In these carbon fibers,, can select and use the carbon fiber that can satisfy its characteristic aptly according to the electrode that uses carbon fiber and the characteristic of battery.
In the above-mentioned carbon fiber, under the occasion of the negative pole that is used to adopt the secondary cell that contains the alkali metal salt nonaqueous electrolytic solution, better with PAN based carbon fiber, pitch-based carbon fiber.,, be handy particularly with the PAN based carbon fiber especially from the good viewpoint of the doping of lithium ion from the doping of alkali metal ion.
Adopt under the occasion of PAN based carbon fiber, the element wt of nitrogen content and phosphorus content ratio is preferably more than 0.07, below 0.22.Be lower than at 0.07 o'clock, carry out crystallization easily, the tendency that has capacity to reduce.And being higher than at 0.22 o'clock, the charing degree becomes insufficient, is difficult to use as the carbon body electrode.Number of elements is than measuring by using willow for example to make Atomic Absorption SpectrophotometerICP commonly used such as the CHN コ-ダ of institute-MT-3 type.
As the manufacture method of PAN based carbon fiber, can enumerate special public clear 37-4405 number, special public clear 44-21175 number, special public clear 47-24185 number, special public clear 51-6244 number, and other many known methods.In the present invention, adopt these methods also can obtain desirable carbon fiber, but, make sintering temperature more than 900 ℃ particularly making under the occasion of this low-crystalline carbon fiber of the present invention, below 1330 ℃ better.When sintering temperature is lower than 900 ℃, can obtain the carbon fiber of low-crystalline, but charing is incomplete, the tendency that is unsuitable for as the carbon body electrode is arranged, and when being higher than 1330 ℃, then promote crystallization, the tendency that has capacity to reduce.Wherein, better with 1000～1300 ℃.And, as obtaining this low-crystalline of the present invention, the method for the carbon fiber of the low degree of orientation, under low-tension or the method for roasting under the state that not have to strain also be effective.
Be used to obtain the precursor autofrettage of carbon fiber, also can adopt known method, adopt wet type spin processes, dry-and wet-type spin processes any can, especially, better with the dry-and wet-type spin processes.Said herein dry-and wet-type spin processes, be meant that the spinning solution of being made by the solvent of the polymer that forms carbon fiber and this polymer spins in air after, import in the coagulating bath immediately, be method preferably thereby obtain method that coagulated yarn stretches again.By import the method in the coagulating bath after spinning solution is spun immediately in air, can alleviate and spin the follow-up spinning tension that draws in the operation that solidifies, especially, can control the spinning tension on the coagulated yarn of early solidification lower, the precursor that the fiber top layer is a high compactness can be obtained thus, and carbon fiber can be produced as the function admirable of electrode for cell.
Have, in will be formed the said method that imports immediately after the spinning solution made from the solvent of polymer and this polymer spins in the coagulating bath by carbon fiber in air, it also is method preferably that coagulating bath is set in the concentration range that can not form cortex again.For the coagulated yarn that solidifies in the coagulating bath in setting the concentration range that can not form cortex, because actual stretching ratio reduces, compare with the precursor that makes by common coagulating bath, can reduce the degree of orientation, therefore we can say, why the present invention has obtained the carbon fiber of the low-crystalline and the low degree of orientation, is owing to form the cause of suitable precursor.
The above-mentioned concentration range that can not form cortex according to the composition of polyacrylonitrile, is promptly graded and different with being copolymerized into according to molecular weight, can open the method for putting down in writing in the clear 61-1197707 communique and sets according to for example special.For example, under the occasion of water, for N, the organic solvent of dinethylformamide, dimethylacetylamide, methyl-sulfoxide etc., the concentration of coagulating agent is in the scope of 60～90 weight %, and for the nitric acid as inorganic solvent, the concentration of coagulating agent is in the scope of 40～50 weight %, for zinc chloride and rhodanate, the concentration of coagulating agent is in the scope of 20～40 weight %.
The carbon fiber that is obtained by roasting also can directly use, and, also can remove the part on top layer by surface treatment.As the method for removing, can enumerate liquid phase oxidation processing and gaseous oxidation processing etc.Specifically, can enumerate in containing the electrolyte aqueous solution of nitrate ion, with carbon fiber as anode, carry out the method that electrochemical oxidation is handled, or in the electrolyte aqueous solution that with the alkali cpd is necessary composition, as anode, carry out the method for electrochemical oxidation processing etc. with carbon fiber.
With carbon fiber of the present invention during as electrode, no matter adopt any form can, can be in the configuration of single shaft direction, or become the structure etc. of cloth and silk shape or felt shape, all be form preferably.As the structure of cloth and silk shape or felt shape etc., can enumerate fabric, compile thing, cotton rope, band, net, felt, paper, nonwoven fabrics, mat etc., consider from aspects such as the character of carbon fiber and electrode characteristics, better with fabric and felt etc.And, under the occasion of single shaft direction configuration, can adopt the neat carbon fiber in metal current collector upper berth at Copper Foil etc., coating has been dissolved and has been constituted the solution of the resin of adhesive, thereby makes carbon fiber be bonded in method on the collector body etc.Have again, under the occasion of cylinder battery, the configuration direction is with along the curl direction of collector body or better perpendicular to the method for configuration carbon fiber on the curl direction, and wherein, the method that disposes perpendicular to curl direction is not owing to peel off the phenomenon that waits so be preferably.
The diameter of used carbon fiber among the present invention should be determined according to the various forms that are easy to make, and preferably, can use the carbon fiber of 1～1000 μ m diameter, 1～20 μ m diameter better.And, also can use the carbon fiber of several different-diameters.
The electrode made from carbon fiber of the present invention can be used as the active electrode of various batteries, be used for primary cell, secondary cell etc. any battery can, have no particular limits.Wherein, can perform well in the negative pole of secondary cell.Especially as secondary cell preferably, can enumerate the secondary cell that adopts the nonaqueous electrolytic solution that contains the such alkali metal salt of lithium perchlorate, lithium fluoroborate, lithium hexafluoro phosphate.
Under the occasion of the nonaqueous electrolytic solution secondary battery that electrode of the present invention is used to contain alkali metal salt, cation doping or anion doped and constitute battery is carried out in utilization in carbon fiber, at this moment, adopting the carbon fiber of cation doping is negative pole, is the anodal battery that constitutes thereby adopt anion doped carbon fiber.Electrode of the present invention can be used for negative or positive electrode according to various characteristics, needn't the two poles of the earth all be electrode of the present invention, and the electrode that constitutes with carbon fiber of the present invention is a negative pole, is positive pole with the electrode of carbon fiber-containing not, also can constitute gratifying embodiment.
When the electrode of carbon fiber-containing is not used for positive pole, can use fiber carbonaceous material in addition as positive pole, in addition, can also use the inorganic compound of artificial or natural powdered graphite, fluorocarbons, metal or metal oxide etc. or organic high molecular compound etc. as anodal.In this case, when the inorganic compound of metal or metal oxide etc. is anodal, utilize cationic doping and take off to be mixed for to be used for discharging and recharging reaction.When organic high molecular compound is anodal, be used for discharging and recharging reaction with taking off to be mixed for by anionic doping.Like this, both can choose the different reactive modes that discharges and recharges according to the difference of material, also can be according to the suitable material of selecting of the necessary anodal characteristic of battery.
As the positive pole of carbon fiber-containing not, can enumerate the inorganic compound, polyacetylene, the poly-conjugated polymer that contain alkali-metal transition metal oxide or transient metal sulfide etc. to styrene, polyaniline, polypyrrole, polythiophene etc.Cross-linked polymer, thionyl chloride with disulphide combination etc. is generally used for the positive pole of secondary cell.Wherein, contain in use under the occasion of secondary cell of nonaqueous electrolytic solution of lithium salts, better adopt the transition metal oxide and the transient metal sulfide of cobalt, nickel, manganese, molybdenum, vanadium, chromium, iron, copper, titanium etc.Especially, because LiCoO
2LiNiO
2Voltage height and energy density big, be best materials used.
Electrolyte as the secondary cell that adopts electrode of the present invention has no particular limits, and can use electrolyte in the past, for example, can enumerate the aqueous solution of acid or alkali or non-aqueous solution etc.Wherein, electrolyte as the secondary cell that constitutes by the above-mentioned nonaqueous electrolytic solution that contains alkali metal salt, can use propene carbonate, ethylene carbonate, gamma-butyrolacton, N-methyl pyrrolidone, acetonitrile, N preferably, dinethylformamide, methyl-sulfoxide, oxolane, 1,3-dioxolanes, methyl formate, sulfolane, oxazolidone, thionyl chloride, 1,2-dimethoxy-ethane, carbonic acid two ethyls and their derivative and mixture etc.As electrolyte contained in the electrolyte, can use the alkali metal particularly halide, perchlorate, rhodanate, borofluoride, fluorophosphate, fluorine arsenate, fluoaluminate, trifluoromethyl sulfate etc. of lithium preferably.
Among the present invention, the discharge capacity of electrode can be measured in accordance with the following methods.At first, carbon fiber as work electrode, as the polarity and the reference utmost point, is made lithium metal to adopt the tripolar cell that contains as the nonaqueous electrolytic solution of electrolytical lithium salts.Carbon fiber uses as electrode with the form that for example is clipped in the stainless screen cloth, as the lithium metal, uses lithium metal foil.By discharging and recharging, measure the discharge capacity of electrode with this tripolar cell.Method as charging and discharge generally has constant potentiometry and constant current anodizing process, adopts constant current anodizing process herein.That is, charge, become 0V(vs.Li up to the current potential of work electrode with constant current
+/ Li), then, discharge with constant current again, become 1.5V(vs.Li up to the current potential of work electrode
+/ Li), the electric current of charging and discharge is per unit carbon fiber weight 40mA/g.According to discharging needed electric weight and obtain discharge capacity (mAh/g) this moment as the weight of the carbon fiber of work electrode.
Purposes as the secondary cell that uses electrode of the present invention, utilize it owing to the feature in light weight and high-energy-density that capacity has greatly, can be widely used for carrying of gamma camera, PC, word processor, miniature radio-cassette player, portable telephone etc. with in the small electronic apparatus.
Embodiment
Enumerate embodiment below and be described more specifically the present invention.Should illustrate that the present invention is not subjected to the qualification of these embodiment.
Embodiment 1
To the degree of orientation of (400) is that 92% polyacrylonitrile fibre is in air and do not have under the state of tension, under 200 ℃ to 250 ℃, carry out flame treatment, then in nitrogen and under the state that does not have to strain,, make carbon fiber thus 1100 ℃ of following roastings 10 minutes.Adopt wide-angle x-ray diffraction (computing method) to measure the degree of orientation of this carbon fiber.The degree of orientation of being tried to achieve this carbon fiber by formula (2) is 77.5%, and trying to achieve crystallite thickness Lc by formula (1) is 14.0
Then, above-mentioned carbon fiber is clipped in the stainless screen cloth of collector body, makes electrode, the evaluation of charging.Electrolyte adopts the propylene carbonate that contains the 1M lithium perchlorate, and the polarity and the reference utmost point adopt metallic lithium foil, estimates by the tripolar cell that constitutes thus.With the current density of per unit carbon fiber weight is that the constant current charge of 40mA/g is to OV(vs.Li
+/ Li).The quantity of electric charge that discharges again after being finished by charging is obtained the discharge capacity of carbon fiber electrode, is 410mAh/g.
Embodiment 2
By the method identical polyacrylonitrile fibre is carried out after anti-combustion handles with embodiment 1, not have under the state of straining, in nitrogen atmosphere, the roasting temperature about 1200 ℃ 10 minutes.
Measure the degree of orientation of this carbon fiber with wide-angle x-ray diffraction (computing method).The degree of orientation of being tried to achieve this carbon fiber by formula (2) is 77.8%.Trying to achieve crystallite thickness Lc by formula (1) is 15.0
Then, use the method identical with embodiment 1 to measure the discharge capacity of above-mentioned carbon fiber, the discharge capacity of this moment is 390mAh/g.
Embodiment 3
By the method identical polyacrylonitrile fibre is carried out after anti-combustion handles with embodiment 1, under the state of tension, in nitrogen atmosphere, the roasting temperature about 1200 ℃ 5 minutes.
Adopt wide-angle x-ray diffraction (computing method) to measure the degree of orientation of this carbon fiber.The degree of orientation of this carbon fiber of being obtained by formula (2) is 81.3%.The crystallite thickness Lc that is obtained by formula (1) is 15.8
Then, use the method identical with embodiment 1 to measure the discharge capacity of above-mentioned carbon fiber, the discharge capacity of this moment is 380mAh/g.
Comparative example 1
By the method identical polyacrylonitrile fibre is carried out after anti-combustion handles, under the state of tension, nitrogen atmosphere and 1700 ℃ of following roastings 5 minutes with embodiment 1.
Adopt wide-angle x-ray diffraction (computing method) to measure the degree of orientation of this carbon fiber.The degree of orientation of being tried to achieve this carbon fiber by formula (2) is 82.0%.Trying to achieve crystallite thickness Lc by formula (1) is 21.0
Then, use the method identical with embodiment 1 to measure the discharge capacity of above-mentioned carbon fiber, the discharge capacity that at this moment records is 240mAh/g.
Embodiment 4
Li/Co=1/1 takes by weighing commercially available lithium carbonate (Li in molar ratio
2CO
3) and cobalt carbonate hydroxide (2CoCO
33Co(OH)
2), it is mixed with ball mill, 900 ℃ of following heat treatments 20 hours, obtain LiCoO thus then
2It is pulverized with ball mill, be mixed into Delanium, as the polyvinylidene fluoride (PVdF) of adhesive, as the N-methyl pyrrolidone of solvent, by weight LiCoO as electric conducting material
2In the mixture of/Delanium/PVdF=80/15/5, modulate anodal slurries thus, coat these slurries on the aluminium foil and carry out drying, compacting, obtain positive pole.
With the carbon fiber electrically made among the embodiment 1 negative pole very, be placed between porous matter polypropylene film (セ Le ガ-De #2500, ダ ィ セ Le chemistry (strain) system) spacer, be superimposed with the above-mentioned positive pole of making, make secondary cell.Electrolyte adopts the propylene carbonate that contains the 1M lithium perchlorate.
To the evaluation of charging of the secondary cell of above-mentioned making.With the current density of per unit carbon fiber weight is that the constant current charge of 40mA/g is to 4.3V.Obtain the discharge capacity of this secondary cell by the quantity of electric charge of discharge after the charging, to being used for the per unit carbon fiber weight of this battery, discharge capacity is 380mAh/g.
Comparative example 2
Adopt carbon fiber electrode that comparative example 1 makes as negative pole, make secondary cell by the method identical with embodiment 4.To being used for the per unit carbon fiber weight of this battery, discharge capacity is 200mAh/g.
Embodiment 5
Polyacrylonitrile fibre is carried out anti-combustion handle under 200 ℃ to 250 ℃ in air, carbon fiber is made in then 1100 ℃ of following roastings 20 minutes in nitrogen thus.The resistivity of being tried to achieve this carbon fiber by formula (3) is 3.0 * 10
-3Ω cm.
Then, adopt the method identical with embodiment 1 to measure the discharge capacity of above-mentioned carbon fiber, recording its discharge capacity is 400mAh/g.And, be the constant current of 1A/g when discharging with the current density of per unit carbon fiber weight, the discharge capacity of carbon fiber electrode is 340mAh/g.
Embodiment 6
By the method identical Dralon is carried out anti-combustion and handle with embodiment 1, then, in nitrogen atmosphere, 1200 ℃ of left and right sides roastings 10 minutes.The resistivity of this carbon fiber of being obtained by formula (3) is 2.0 * 10
-3Ω cm.
Then, adopt the method identical with embodiment 1 to measure the discharge capacity of above-mentioned carbon fiber, recording its discharge capacity is 380mAh/g.And, be the constant current of 1A/g when discharging with the current density of per unit carbon fiber weight, the discharge capacity of carbon fiber electrode is 320mAh/g.
Embodiment 7
By the method identical with embodiment 1 polyacrylonitrile fibre is carried out anti-combustion and handle, in nitrogen atmosphere, 1200 ℃ of left and right sides roastings 20 minutes, the resistivity of being obtained this carbon fiber by formula (1) was 1.8 * 10 then
-3Ω cm.The crystallite thickness Lc that is obtained this carbon fiber by formula (2) is 16
Then, adopt the method identical with embodiment 1 to measure the discharge capacity of above-mentioned carbon fiber, recording this discharge capacity is 380mAh/g.And, be the constant current of 1A/g when discharging with the current density of per unit carbon fiber weight, the discharge capacity of carbon fiber electrode is 330mAh/g.
Comparative example 3
By the method identical with embodiment 1 Dralon is carried out anti-combustion and handle, then, 1700 ℃ of left and right sides roastings 10 minutes, the resistivity of being obtained this carbon fiber by formula (1) was 1.4 * 10 in nitrogen atmosphere
-3Ω cm.The crystallite thickness Lc that is obtained this carbon fiber by formula (2) is 21
Then, adopt the method identical with embodiment 1 to measure the discharge capacity of above-mentioned carbon fiber, discharge capacity at this moment is 280mAh/g.And, be the constant current of 1A/g when discharging with the current density of per unit carbon fiber weight, the discharge capacity of carbon fiber electrode is 200mAh/g.
Comparative example 4
Commercially available pitch coke is pulverized, obtained the carbon dust that average grain diameter is about 10 μ m.The resistivity of this powder is 3.0 * 10
-3Ω cm, crystallization thickness Lc is 274.
Then, in above-mentioned pitch coke powder, add polyvinylidene fluoride (PVDF) 10 weight portions, use N-N-methyl-2-2-pyrrolidone N-(NMP), make slurries as solvent.These slurries are coated on the aluminium foil, dry then, make electrode, the evaluation of charging.Electrolyte adopts the propylene carbonate that contains the 1M lithium perchlorate, and the polarity and the reference utmost point adopt metallic lithium foil, estimate by the tripolar cell of making thus.Current density with per unit carbon weight is the constant current of 40mA/g, charges to 0V(vs.Li
+/ Li), then, be discharged to 1.5V(vs.Li
+/ Li).When being the constant current discharge of 40mA/g with the current density of per unit carbon weight, the discharge capacity of carbon electrode is 260mAh/g, and when being the constant current discharge of 1A/g with the current density of per unit carbon weight, the discharge capacity of carbon electrode is 100mAh/g,
Embodiment 8
Li/Co=1/1 takes by weighing commercially available lithium carbonate (Li in molar ratio
2CO
3) and cobalt carbonate hydroxide (2CoCO
33Co(OH)
2), it is mixed with ball mill, 900 ℃ of following heat treatments 20 hours, obtain LiCoO thus then
2It is pulverized with ball mill, is mixed into Delanium as electric conducting material, be used as adhesive polyvinylidene fluoride (PVdF), be used as the N-methyl pyrrolidone of solvent, by weight LiCoO
2In the mixture of/Delanium/PVdF=80/15/5, modulate anodal slurries thus, these slurries are coated on the aluminium foil, drying, compacting obtain positive pole.
With the carbon fiber electrically made among the embodiment 7 negative pole very, be placed between porous matter polypropylene film (セ Le ガ-De #2500, ダ ィ セ Le chemistry (strain) system) spacer, be superimposed with the above-mentioned positive pole of making, make secondary cell.Electrolyte adopts the propylene carbonate that contains the 1M lithium perchlorate.
To the evaluation of charging of the secondary cell of above-mentioned making.With the current density of per unit carbon fiber weight is that the constant current of 40mA/g charges to 4.3V.Obtain the discharge capacity of this secondary cell by the quantity of electric charge of discharge after the charging, to being used for the per unit carbon fiber weight of this battery, discharge capacity is 380mAh/g.
Comparative example 5
The carbon fiber electrode of making in the comparative example 3 is used as negative pole, makes secondary cell by the method identical with embodiment 8.The discharge capacity of this carbon fiber electrode, to the per unit weight of the carbon fiber that is used for this battery, discharge capacity is 200mAh/g.
Embodiment 9
To the degree of orientation of (400) is 92% polyacrylonitrile fibre, in air and do not have under the state of tension, carries out anti-combustion and handle under 200 ℃ to 250 ℃, then, in nitrogen and under the state that does not have to strain,, make carbon fiber thus 1100 ℃ of following roastings 5 minutes.The crystallite thickness Lc of this carbon fiber of being obtained by formula (1) is 13.5
CHN コ-ゲ-the nitrogen content of MT-3 type mensuration of making gained of willow is 0.149 with the ratio of phosphorus content.
The discharge capacity that adopts the method identical with embodiment 1 to record above-mentioned carbon fiber is 420mAh/g.
Comparative example 6
Sintering temperature is 1500 ℃, in addition, adopts the method making carbon fiber identical with embodiment 9.The crystallite thickness Lc of this carbon fiber of being obtained by formula (1) is 18
The ratio of the nitrogen content phosphorus content of measuring by the method identical with embodiment 9 is 0.031.
The discharge capacity that adopts the method identical with embodiment 1 to record above-mentioned carbon fiber is 250mAh/g.
Embodiment 10
Use the carbon fiber that obtains among the embodiment 1, adopt and contain 1M LiBF
4Propylene carbonate and 1,1: 1 mixed solution of 2-dimethoxy-ethane is as electrolyte, in addition, adopts the method identical with embodiment 1 to measure discharge capacity, the discharge capacity that records at this moment is 400mAh/g.
The present invention can provide with the electrode for cell of fibrous organic substance sintered body as active electrode, and the high-capacity secondary battery of using kind electrode, is used for the electrode for cell and the manufacture method thereof of this battery.
Claims (25)
1, a kind of electrode for cell is characterized in that, it adopts the crystallite thickness that is recorded by X-ray diffraction 13
More than, 17
Following carbon fiber.
2, the electrode for cell described in the claim 1 is characterized in that, the crystallite thickness that is recorded by X-ray diffraction is 14
More than, 16
Below.
3, the electrode for cell described in the claim 1 or 2 is characterized in that, the said degree of orientation is more than 70%, below 85%.
4, the electrode for cell of claim 1～3 described in any one is characterized in that its discharge capacity is more than 350mAh/g.
5, the electrode for cell of claim 1～4 described in any one is characterized in that its resistivity is 1.0 * 10
-3More than the Ω cm, 4.0 * 10
-3Below the Ω cm.
6, the electrode for cell of claim 1～5 described in any one is characterized in that its resistivity is 1.0 * 10
-3More than the Ω cm, 2.5 * 10
-3Below the Ω cm.
7, the electrode for cell of claim 1～6 described in any one is characterized in that said carbon fiber is fibrous organic substance sintered body.
8, the electrode for cell described in the claim 7 is characterized in that, said carbon fiber is the polyacrylonitrile based carbon fiber.
9, the electrode for cell described in the claim 1～8 is characterized in that, said nitrogen content compares more than 0.07, below 0.22 with the element wt of phosphorus content.
10, the electrode for cell of claim 1～9 described in any one is characterized in that, this electrode is used as negative pole.
11, the electrode for cell of claim 1～10 described in any one is characterized in that, said carbon fiber forms folk prescription to arrange body.
12, a kind of secondary cell is characterized in that, it is to make with the electrode for cell of claim 1～11 described in any one.
13, the secondary cell described in the claim 12 is characterized in that, it has adopted the non-aqueous electrolyte that contains lithium salts.
14, the secondary cell described in the claim 12 or 13 is characterized in that, it adopts tetrafluoride boron as electrolyte.
15, the secondary cell of claim 11～14 described in any one is characterized in that, uses transition metal oxide on positive pole.
16, the secondary cell of claim 11～15 described in any one is characterized in that said transition metal is selected from any among Li, Ni, Mn and the Fe.
17, a kind of manufacture method of electrode for cell is characterized in that, in the manufacture method of the electrode for cell that uses carbon fiber, the sintering temperature of said carbon fiber is more than 900 ℃, below 1330 ℃.
18, the manufacture method of the electrode for cell described in the claim 17 is characterized in that, said sintering temperature is more than 1000 ℃, below 1300 ℃.
19, the manufacture method of the electrode for cell described in the claim 17 is characterized in that, said carbon fiber is fibrous organic substance sintered body.
20, the manufacture method of the electrode for cell of claim 17～19 described in any one is characterized in that said carbon fiber is the polyacrylonitrile based carbon fiber.
21, the manufacture method of the electrode for cell of claim 17～20 described in any one is characterized in that, is being made by carbon fiber in the manufacture method of electrode, and said carbon fibre precursor is that the coagulated yarn that will be obtained by the dry-jet wet-spinning method stretches and forms.
22, the manufacture method of the electrode for cell described in the claim 21 is characterized in that, said coagulating bath is set in the concentration range that can not form cortex.
23, a kind of manufacture method of electrode for cell is characterized in that, handles the good carbon fiber of roasting, removes the part on top layer.
24, the manufacture method of the electrode for cell described in the claim 23 is characterized in that, said method of removing a top layer part is in containing the electrolyte aqueous solution of nitrate ion, said carbon fiber is carried out electrochemical oxidation as anode handle.
25, the manufacture method of the electrode for cell described in the claim 23, it is characterized in that, said method of removing a top layer part is in the electrolyte aqueous solution of alkali cpd as neccessary composition, said carbon fiber is carried out electrochemical oxidation as anode handle.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP152408/93 | 1993-06-23 | ||
| JP15240893 | 1993-06-23 | ||
| JP161639/93 | 1993-06-30 | ||
| JP161637/93 | 1993-06-30 | ||
| JP190352/93 | 1993-07-30 | ||
| JP223476/93 | 1993-09-08 | ||
| JP22347693 | 1993-09-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1111074A true CN1111074A (en) | 1995-11-01 |
Family
ID=26481340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94190416A Pending CN1111074A (en) | 1993-06-23 | 1994-06-23 | Cell electrode, secondary cell using the cell electrode, and method for manufacturing the cell electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1111074A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101371381A (en) * | 2006-01-23 | 2009-02-18 | 奈克松有限公司 | A method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| CN111549573A (en) * | 2020-05-09 | 2020-08-18 | 中国科学院山西煤炭化学研究所 | Carbon paper for proton exchange membrane hydrogen fuel cell and preparation method thereof |
-
1994
- 1994-06-23 CN CN94190416A patent/CN1111074A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101371381A (en) * | 2006-01-23 | 2009-02-18 | 奈克松有限公司 | A method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| US9583762B2 (en) | 2006-01-23 | 2017-02-28 | Nexeon Limited | Method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| CN103560226B (en) * | 2006-01-23 | 2017-04-12 | 奈克松有限公司 | A method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| CN111549573A (en) * | 2020-05-09 | 2020-08-18 | 中国科学院山西煤炭化学研究所 | Carbon paper for proton exchange membrane hydrogen fuel cell and preparation method thereof |
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