CN1471191A - Non-aqueous electrolytic solution secondary cell - Google Patents
Non-aqueous electrolytic solution secondary cell Download PDFInfo
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- CN1471191A CN1471191A CNA021264686A CN02126468A CN1471191A CN 1471191 A CN1471191 A CN 1471191A CN A021264686 A CNA021264686 A CN A021264686A CN 02126468 A CN02126468 A CN 02126468A CN 1471191 A CN1471191 A CN 1471191A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Stabilized power can be obtained no matter what discharging depth of the invented battery is, and it is easy to detect residual capacity. The graphite granule G in specific grain size and petroleum asphalt are mixed and then sintered at about 1000 deg.C under atmosphere of inert gases. Then, crushing and sieving processes are carried out to obtain the binding granule C in anticipant grain size being able to bind non crystalline carbon A and utilized among graphite granules G. the negative pole made from binding granule C served as negative active material and the positive pole made from lithium manganese served as positive active material are rolled through separator so as to form the rolled cluster. The part of non-crystalline carbon A is bound among graphite granules G increases apparent density.
Description
Technical field
The present invention relates to a kind of nonaqueous electrolytic solution secondary battery, being specifically related to the electrode group soaks in nonaqueous electrolytic solution and is contained in the battery case, but reach the nonaqueous electrolytic solution secondary battery more than 10 seconds more than the continuous discharge 50W, wherein, positive pole and negative pole in the electrode group dispose by separator, above-mentioned positive pole is meant the positive pole of complex Li-Mn-oxide as positive active material, and above-mentioned negative pole is meant material with carbon element as negative electrode active material and with the negative pole of resin combination as the negative pole bond.
Background technology
The nonaqueous electrolytic solution secondary battery that with the lithium rechargeable battery is representative is brought into play the advantage that it has high-energy-density, mainly as the power supply of the portable set of VTR camera, notebook-sized personal computer, portable phone etc.The internal structure of this battery adopts takeup type shown below usually.The positive pole of this battery and negative pole are active material are coated to band shape on the metal forming, and make and anodally directly contact mutually with negative pole in order to sandwich separator, and section is wound into helical form, thereby form coiling group.This coiling group is contained in the cylindrical battery jar as battery case, seals after injecting electrolyte.
General cylindrical lithium ion secondary battery is called as 18650 types, and it is of a size of diameter 18mm, height 65mm, and this battery is widely used as small-sized civilian lithium ion battery.With high power capacity, long-life be the cobalt acid lithium of feature mainly as the positive active material of 18650 type lithium rechargeable batteries, the battery capacity of 18650 type batteries is about 1.3Ah～1.7Ah, the power of battery is about the 10W degree.
On the other hand, in auto industry circle, in order to solve environmental problem, quickened not have and discharged electric automobile (EV) gas, that power source only limited to fully battery, and with explosive motor and the two exploitation as hybrid (electronic) automobile of power source of battery, and wherein a part has reached the practicability stage.
Certainly, this battery request as electric car power supply has high power, high-octane characteristic, and just receives publicity as the lithium ion battery that can satisfy the battery of this requirement.In order to popularize electric automobile, must reduce battery cost.For this reason, need battery material cheaply, for example, aspect positive active material, the oxide of resourceful manganese just is being subjected to special concern, and has done improvement for the high performance of realizing battery.And, only provide the battery for electric automobile of power source by battery fully as electric power, not only require and every charging directly related high power capacity of continuous operating range once, but also requirement influences the high power of the acceleration performance of electric automobile etc.
Regardless of the residual capacity of battery, obtain stable rideability in order to make electric automobile, must obtain stable electrical power from battery.That is to say, preferably, even as depth of discharge (the Depth of Discharge of expression discharge capacity with the ratio of the rated capacity of battery, call DOD in the following text) when being in dark state, the power of battery can extremely not descend yet, even and recharge use battery, the power that takes out from battery can not change yet.
On the other hand, when the residual capacity of battery tails off, be necessary easily to detect residual capacity, make the driver of electric automobile can discern residual capacity.For example, for the automobile of fossil fuels such as gasoline, light oil as power source, this is equivalent to detect the residual fuel amount in the fuel tank and it is presented at mechanism on the fuel meter.
Summary of the invention
In view of the foregoing, the purpose of this invention is to provide a kind of nonaqueous electrolytic solution secondary battery, no matter how depth of discharge can both obtain firm power to this battery, and can easily detect residual capacity.
To achieve these goals, the invention provides a kind of nonaqueous electrolytic solution secondary battery, wherein, the electrode group is soaked in nonaqueous electrolytic solution and is contained in the battery case, and positive pole and negative pole in this electrode group dispose by separator, wherein, described positive pole is used as positive active material with complex Li-Mn-oxide, and described negative pole is used as the negative pole bond with material with carbon element as negative electrode active material and with resin combination, but and reach more than 10 seconds more than this battery continuous discharge 50W, it is characterized in that, above-mentioned material with carbon element be between graphite particle with the amorphous carbon combination in conjunction with particle.
In the present invention, use complex Li-Mn-oxide as the positive pole of positive active material, with the negative pole of material with carbon element as negative electrode active material.By will be between graphite particle with the amorphous carbon combination in conjunction with particle as material with carbon element because the part of the amorphous carbon that combines between the graphite particle has been increased the apparent density of material with carbon element, thus can be from whole negative electrode active material current collection expeditiously.Therefore, can realize the nonaqueous electrolytic solution secondary battery no matter how DOD can both obtain firm power.In addition, owing to be well known that: with amorphous carbon as having linear relationship between the DOD of the general lithium secondary battery of negative electrode active material and the voltage, therefore, even the nonaqueous electrolytic solution secondary battery of the present invention that also can obtain firm power when DOD is in dark state is because of comprising the amorphous carbon as negative electrode active material, thereby, can easily detect residual capacity by measuring voltage.
In this case, if the flaky graphite particle as in conjunction with the graphite particle of particle, then can obtain the good nonaqueous electrolytic solution secondary battery of initial stage power.And if be set to 4～24% in conjunction with the ratio of the amorphous carbon phase in the particle, even then DOD deepens, it is few that the power of battery is descended, even and reuse battery, also can keep initial discharge capacity.And if be set to 14～40 μ m in conjunction with the average grain diameter of particle, then first efficiency for charge-discharge and initial stage power are all good, even and reuse battery, also can keep initial stage power.And if the average grain diameter of graphite is set to 3～16 μ m, then first efficiency for charge-discharge and initial stage power are all good, even and reuse battery, also can keep initial stage power.Therefore, this during when using in conjunction with particle and as the Thermocurable plasticization polyvinyl alcohol resin constituent of bond, even after repeating charge and discharge cycles, regardless of DOD, also can keep firm power, its level and charge and discharge cycles are before much at one.
In addition, be meant but " reach more than 10 seconds more than the continuous discharge 50W ", when on accelerator (throttle) pedal of stepping at electric automobile when quickening, must keep the above continuous power of 50W and reach more than 10 seconds, for, for example, if battery with the following continuous power of 20W, the series connection and/or the quantity in parallel that then are loaded in the battery on the electric automobile increase, and therefore, in fact are not suitable for being loaded on the electric automobile.
Description of drawings
Fig. 1 is the key diagram in conjunction with particle that concept nature illustrates carbon material used as anode of the present invention; And
Fig. 2 is the profile that can use the column lithium ion battery of embodiments of the present invention.
Embodiment
Hereinafter with reference to accompanying drawing, describe the present invention being applied to the execution mode that electric automobile (EV) loads with column lithium ion battery.
(making of positive plate)
The LiMn2O4 as positive active material (LiMn2O4) powder of the about 20 μ m of average grain diameter, as the graphite of the about 6 μ m of the average grain diameter of first electric conducting material, as the acetylene black of second electric conducting material and as the poly-difluoroethylene (PVdF) of bonding agent in mass ratio with 85: 8: 2: 5 ratio is mixed, obtain slurry to the N-N-methyl-2-2-pyrrolidone N-(NMP) and the mixing that wherein add as dispersion solvent, this slurry is coated to the two sides of the aluminium foil that thickness is 20 μ m (positive electrode collector).The coating amount of the mixture except the NMP (cathode mix) is 290g/m
2At this moment, positive plate longitudinally a lateral margin leave the uncoated part that width is 50mm.Afterwards, carrying out drying, compacting and cutting obtains the wide 300mm of cathode mix coating part, long 6.33mm, cathode mix to apply part thick is the banded positive plate of 219 μ m (except the thickness of aluminium foil).The apparent density of positive-electrode mixture layer is set to 2.65g/cm
3In the slurry uncoated part of positive plate, do otch, the otch remainder is used as guide plate (with reference to the symbol 9 of Fig. 2).And, the interval between the adjacent guide plate is set at 50mm, be 10mm with the width setup of guide plate.
(making of carbon material used as anode)
The graphite particle that will have following regulation particle diameter mixes with petroleum asphalt, then in containing inert gas atmosphere such as nitrogen, argon, carry out after the sintering with about 1000 ℃, by pulverizing and screening, obtain between graphite particle with the expectation particle diameter of amorphous carbon combination in conjunction with particle.For obtain expeditiously the expectation particle diameter in conjunction with particle, also can pulverize and sieve graphite in advance.Graphite also can adopt the following manner manufacturing: in inert gas atmosphere such as nitrogen, argon, after material resin bodies such as petroleum asphalt being carried out sintering with about 1000～1400 ℃, pulverizing, in identical atmosphere, heat-treat with about 3000 ℃.Also can use as described below commercially available prod.As shown in Figure 1, the carbon material used as anode of making by heat treatment like this in conjunction with between the graphite particle G of particle C with amorphous carbon A combination.In conjunction with the amount of the amorphous carbon A among the particle C can be by the graphite particle G before dropping into sintering quality and sintering after the quality that combines particle C between difference obtain.And, the percentage in conjunction with the quality of particle C is obtained in conjunction with the quality that the ratio (calling the amorphous carbon one after another in the following text) of the amorphous carbon A among the particle C can be by amorphous carbon A.In addition, graphite particle G and in conjunction with the average grain diameter of particle C can be by mensuration such as laser diffraction formula particle size distribution meters, obtain.
(making of bond resin combination)
Thermocurable plasticization polyvinyl alcohol resin adopts and first resinous principle of being made up of the Thermocurable polyvinyl alcohol resin to be mixed with second resinous principle of being made up of the acrylic resin plasticizer and is dissolved in the suitable solvent (in the present embodiment, be meant the N-N-methyl-2-2-pyrrolidone N-, call NMP in the following text) resulting material.Thermocurable polyvinyl alcohol resin as first resinous principle can adopt following manner to obtain: in organic solvents such as NMP, in the presence of catalyst such as triethylamine, and under the anhydrous actually state, the cyclic acid anhydride of the polyvinyl alcohol resin that makes about 2000 degree of average degree of polymerization and for example succinyl oxide etc. reacts.Preferably, the reaction ratio of polyvinyl alcohol resin and cyclic acid anhydride is set to: for the alcoholic hydroxyl of the polyvinyl alcohol resin of 1 equivalent, about 0.1 equivalent of the acid anhydride base of cyclic acid anhydride.
Can use the reactant of lauryl acrylate/acrylic copolymer and difunctionality type epoxy resin as the acrylic resin plasticizer of second resinous principle.
The synthetic method of the Thermocurable plasticization polyvinyl alcohol resin constituent that uses in the present embodiment is as follows.
First resinous principle adopts following manner to synthesize: 51g polyvinyl alcohol, 650gNMP and the 10g toluene input of saponification degree about 98% are equipped with in the divided flask of mixer, thermometer, cooling water pipe, distillation cascade and nitrogen ingress pipe, when nitrogen bubbles and stirs, spent about 30 minutes to be heated to 195 ℃ then.With 195 ℃ of temperature insulations 2 hours, by making refluxing toluene, make the moisture azeotropic, so that remove the moisture in the flask.Then, remove toluene, this mixture is cooled to 120 ℃, and when when 120 ℃ temperature, being incubated, add the 7.7g succinyl oxide, make and carry out reaction in 1 hour (for the alcoholic hydroxyl of the polyvinyl alcohol of 1 equivalent, about 0.07 equivalent of anhydride group).After cool to room temperature, can obtain the nmp solution of the about 8 quality % of first resinous principle.
Second resinous principle adopts following manner to synthesize: with the 110g no-solvent type lauryl acrylate/acrylic copolymer of weight average molecular weight about 3100 and 71g bisphenol A type epoxy resin (for the carboxyl of the no-solvent type lauryl acrylate/acrylic copolymer of 1 equivalent, epoxy radicals is about 2 equivalents) drop into and to be equipped with in the divided flask of mixer, thermometer, cooling water pipe, distillation cascade and nitrogen ingress pipe, when nitrogen bubbles and stirs, spent about 15 minutes to be heated to 150 ℃ then.With 150 ℃ of temperature insulations 2 hours, after reacting then,, make cool to room temperature to wherein adding 78gNMP, obtain the nmp solution of the about 70 weight % of second resinous principle.
With the nmp solution of the nmp solution of first resinous principle, 8 quality % and the about 70 weight % of second resinous principle mass conversion according to each resinous principle, ratio with 100: 10 is mixed, and obtains the nmp solution of Thermocurable plasticization polyvinyl alcohol resin constituent.
(making of negative plate)
In 92 wt parts of above-mentioned carbon material used as anode, add PVdF as 8 wt parts of bond, and then in it, add as the NMP of dispersion solvent and mix, to generate slurry, this slurry is coated on the two sides of the rolled copper foil that thickness is 10 μ m (negative electrode collector).Perhaps, the nmp solution that in 92 wt parts of above-mentioned carbon material used as anode, mixes above-mentioned Thermocurable plasticization polyvinyl alcohol resin constituent, and the total amount that makes first resinous principle and second resinous principle is 8 wt parts, and mixing is coated to slurry on the two sides of the rolled copper foil that thickness is 10 μ m (negative electrode collector) to generate slurry.The coating amount of the mixture except the NMP (negative pole mixture) is 97g/m
2Negative plate longitudinally a lateral margin leave the uncoated part that width is 50mm.Afterwards, carry out drying, compacting and cutting, it is the banded negative plate of 139 μ m that the wide 305mm of acquisition negative pole mixture coating part, long 6.51m, negative pole mixture apply part thick.At this moment, by compacting compression negative plate, the voidage that makes the negative pole mixture layer is about 35%.Afterwards, with 150 ℃ use Thermocurable plasticization polyvinyl alcohol resin is carried out 16 hours vacuumize and heat treatment as the negative pole of bond.Same with positive plate, in the slurry uncoated part of negative plate, do otch, the otch remainder is used as guide plate (with reference to the symbol 9 of Fig. 2).And, the interval between the adjacent guide plate is set at 50mm, be 10mm with the width setup of guide plate.
(making of battery)
The banded positive plate and the negative plate of above-mentioned making are reeled by the separator with microporous polyethylene system of wide 310mm, thick 40 μ m, so that the not directly contact mutually of this two-plate.At this moment, the guide plate 9 of positive plate and negative plate is configured in respectively on the group's 6 that reels the both ends of the surface of mutual opposite side.With the group's 6 that reels diameter adjustment is 64 ± 0.3mm.In addition, the length setting of negative plate is become the long 18cm of length than positive plate, so that positive plate the group that reels interior week on coiling direction, do not exceed the scope of negative plate, and make positive plate on coiling direction, also not exceed the scope of negative plate at the group's that reels most peripheral.And, the width setup of negative pole mixture coating part is become than the cathode mix coating long 5mm of width partly, so that cathode mix coating part does not exceed the scope of negative pole mixture coating part yet on the direction vertical with coiling direction.
As shown in Figure 2, make guide plate 9 distortion of deriving from positive plate, and all guide plates are integrated near the side face of the overhanging flange section 7 of the integral body on every side that is similar to the pole (anodal outside terminal 1) on the extended line that is positioned at a core 11, after making guide plate 9 and flange section 7 contacts, guide plate 9 is connected and be fixed on the side face of flange section 7 by ultrasonic bonding.And, the mode of carrying out and anodal outside terminal 1 and identical of the attended operation between the negative outer terminal 1 ' and the guide plate 9 of deriving from negative plate from the attended operation between the guide plate 9 of positive plate derivation.
Afterwards, on the whole peripheral surface of the flange section 7 of anodal outside terminal 1 and negative outer terminal 1 ', apply insulation-coated 8.This insulation-coated 8 also is applied to the group's 6 that reels outer peripheral face on full week.A kind of adhesive tape of these insulation-coated 8 uses, the base material of this adhesive tape is a polyimides, and the adhesive that coating is made of hexamethyl acrylate (Hexameta-acrylate) on one face.The side face of this adhesive tape from flange section 7 begun to form insulation-coated 8 to the group's 6 that reels outer peripheral face around several layers.Winding number with insulation-coated 8 be adjusted to make the group 6 that reels maximum gauge partly for there being insulation-coated 8 part, and this maximum gauge is set for more smaller than the internal diameter of the battery case 5 of stainless steel, in the group's 6 insertion battery cases 5 of will reeling.The external diameter of battery case 5 is 67mm, and internal diameter is 66mm.
Next, second ceramic washer 3 ' is embedded the top respectively and constitute the pole of anodal outside terminal 1 and the pole that the top constitutes negative outer terminal 1 '.Wherein, second ceramic washer 3 ' is the part that the back side with discoid battery cover 4 of oxidation aluminum contacts, and its thickness is that 2mm, internal diameter are that 16mm, external diameter are 25mm.And, be that 2mm, internal diameter are that 16mm, external diameter are that flat first ceramic washer 3 of 28mm is placed on the battery cover 4 with the thickness of oxidation aluminum, and anodal outside terminal 1 and negative outer terminal 1 ' inserted first ceramic washer 3 respectively.Afterwards, all end faces of battery cover 4 are cooperated with the opening portion of battery case 5, both sides' whole contact portion is carried out laser welding.At this moment, anodal outside terminal 1 and negative outer terminal 1 ' connect the hole that is formed centrally in battery cover 4, protrude into the outside of battery cover 4.Afterwards, first ceramic washer 3 and the metal washer 14 more level and smooth than the bottom surface of metal nuts 2 are embedded anodal outside terminal 1 and negative outer terminal 1 ' in this order respectively.In addition, battery cover 4 is provided with along with inner pressure of battery rises and the cracking valve 10 as the low mechanism of internal drop of cracking.The cracking pressure of cracking valve 10 is set at 1.3 * 10
6～1.8 * 10
6Pa.
Next, nut 2 is screwed to respectively on anodal outside terminal 1 and the negative outer terminal 1 ', is fixed between flange section 7 and the nut 2 so that battery cover 4 is tightened by second ceramic washer 3 ', first ceramic washer 3 and metal washer 14.At this moment, tighten the torque value and be about 7Nm.In addition, before the work of tightening was finished, metal washer 14 did not rotate.In this state, the O shape of making by the rubber (EPDM) between battery cover 4 back sides and flange section 7 is encircled 16 compression, mainly being interdicted from atmosphere by the group's 6 generating important documents that constitute of reeling of battery case 5 inside.
Afterwards, inject in the battery case 5 from the liquid injection port 15 that is located on the battery cover 4, seal liquid injection port 15 then, finish column lithium ion battery 20 by nonaqueous electrolytic solution with specified quantity.
Nonaqueous electrolytic solution adopts phosphorus hexafluoride acid lithium (LiPF
6) be dissolved into the material that obtains in the mixed solution of forming by 1: 1: 1 volume ratio by this three of vinyl carbonate, dimethyl carbonate and diethyl carbonate by 1 mol.In addition, column lithium ion battery 20 is not provided with the temperature in the battery case 5 and rises and for example PTC (positive temperature coefficient) (the Positive Temperature Coefficient) parts of cut-off current, is not provided with the inner pressure of battery rising yet and cuts off the current cut-off mechanism that is electrically connected.
[embodiment]
Below the embodiment that makes the column lithium ion battery 20 that various changes make according to the shape of the average grain diameter of present embodiment, anticathode material with carbon element (in conjunction with particle C), graphite particle G and average grain diameter and amorphous carbon one after another etc. is described, in addition, for relatively, also the battery to the comparative example made describes.
(embodiment 1)
As shown in table 1 below, in embodiment 1, use average grain diameter be the carbon of 36 μ m in conjunction with particle as carbon material used as anode, this carbon is to be that the centre of 8 μ m is that globular graphite (make, trade name: KMFC) make by Kawasaki Steel (strain) mutually by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 16%.
[table 1]
| In conjunction with particle | ||||
| Particle diameter (μ m) | Graphite | Amorphous carbon one after another (%) | ||
| Kind | Particle diameter (μ m) | |||
| Embodiment 1 | ????36 | ?KMFC | ????8 | ????16 |
| Embodiment 2 | ????33 | ?KMFC | ????8 | ????4 |
| Embodiment 3 | ????40 | ?KMFC | ????8 | ????24 |
| Embodiment 4 | ????33 | ?KMFC | ????8 | ????3 |
| Embodiment 5 | ????40 | ?KMFC | ????8 | ????26 |
| Embodiment 6 | ????42 | ?KMFC | ????8 | ????20 |
| Embodiment 7 | ????14 | ?KMFC | ????5 | ????20 |
| Embodiment 8 | ????12 | ?KMFC | ????5 | ????20 |
| Embodiment 9 | ????36 | Flakey | ????8 | ????16 |
| Embodiment 10 | ????33 | Flakey | ????8 | ????4 |
| Embodiment 11 | ????40 | Flakey | ????8 | ????24 |
| Embodiment 12 | ????33 | Flakey | ????8 | ????3 |
| Embodiment 13 | ????40 | Flakey | ????8 | ????26 |
| Embodiment 14 | ????42 | Flakey | ????8 | ????20 |
| Embodiment 15 | ????14 | Flakey | ????5 | ????20 |
| Embodiment 16 | ????12 | Flakey | ????5 | ????20 |
| Embodiment 17 | ????16 | Flakey | ????3 | ????20 |
| Embodiment 18 | ????16 | Flakey | ????2 | ????20 |
| Embodiment 19 | ????40 | Flakey | ????16 | ????20 |
| Embodiment 20 | ????40 | Flakey | ????18 | ????20 |
| Embodiment 21 | ????36 | ?KMFC | ????8 | ????16 |
| Embodiment 22 | ????36 | Flakey | ????8 | ????16 |
| Comparative example 1 | ????- | ?KMFC | ????16 | ????- |
| Comparative example 2 | ????- | Flakey | ????12 | ????- |
| Comparative example 3 | ????- | KMFC/ noncrystalline | ????16/20 | ????- |
| Comparative example 4 | ????- | KMFC/ カ one ボ ト ロ Application | ????16/20 | ????- |
| Comparative example 5 | ????- | Flakey/noncrystalline | ????12/12 | ????- |
| Comparative example 6 | ????- | Flakey/カ one ボ ト ロ Application | ????12/12 | ????- |
(embodiment 2)
As shown in table 1, in embodiment 2, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 33 μ m in conjunction with particle, and this carbon is to be that the KMFC of 8 μ m makes by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 4%.
(embodiment 3)
As shown in table 1, in embodiment 3, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 40 μ m in conjunction with particle, and this carbon is to be that the KMFC of 8 μ m makes by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 24%.
(embodiment 4)
As shown in table 1, in embodiment 4, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 33 μ m in conjunction with particle, and this carbon is to be that the KMFC of 8 μ m makes by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 3%.
(embodiment 5)
As shown in table 1, in embodiment 5, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 40 μ m in conjunction with particle, and this carbon is to be that the KMFC of 8 μ m makes by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 26%.
(embodiment 6)
As shown in table 1, in embodiment 6, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 42 μ m in conjunction with particle, and this carbon is to be that the KMFC of 8 μ m makes by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 7)
As shown in table 1, in embodiment 7, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 14 μ m in conjunction with particle, and this carbon is to be that the KMFC of 5 μ m makes by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 8)
As shown in table 1, in embodiment 8, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 12 μ m in conjunction with particle, and this carbon is to be that the KMFC of 5 μ m makes by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 9)
As shown in table 1, in embodiment 9, used average grain diameter be the carbon of 36 μ m in conjunction with particle, and this carbon is to be that the flaky graphite of 8 μ m is made by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 16%.
(embodiment 10)
As shown in table 1, in embodiment 10, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 33 μ m in conjunction with particle, and this carbon is by using the flaky graphite making identical with embodiment 9 in conjunction with particle.At this moment, the amorphous carbon one after another is 4%.
(embodiment 11)
As shown in table 1, in embodiment 11, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 40 μ m in conjunction with particle, and this carbon is by using the flaky graphite making identical with embodiment 9 in conjunction with particle.At this moment, the amorphous carbon one after another is 24%.
(embodiment 12)
As shown in table 1, in embodiment 12, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 33 μ m in conjunction with particle, and this carbon is by using the flaky graphite making identical with embodiment 9 in conjunction with particle.At this moment, the amorphous carbon one after another is 3%.
(embodiment 13)
As shown in table 1, in embodiment 13, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 40 μ m in conjunction with particle, and this carbon is by using the flaky graphite making identical with embodiment 9 in conjunction with particle.At this moment, the amorphous carbon one after another is 26%.
(embodiment 14)
As shown in table 1, in embodiment 14, the battery production method is identical with embodiment 1, only used average grain diameter be the carbon of 42 μ m in conjunction with particle, and this carbon is by using the flaky graphite making identical with embodiment 9 in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 15)
As shown in table 1, in embodiment 15, used average grain diameter be the carbon of 14 μ m in conjunction with particle, and this carbon is to be that the flaky graphite of 5 μ m is made by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 16)
As shown in table 1, in embodiment 16, the battery production method is identical with embodiment 15, only used average grain diameter be the carbon of 12 μ m in conjunction with particle, and this carbon is by using the flaky graphite making identical with embodiment 15 in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 17)
As shown in table 1, in embodiment 17, used average grain diameter be the carbon of 16 μ m in conjunction with particle, and this carbon is to be that the flaky graphite of 3 μ m is made by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 18)
As shown in table 1, in embodiment 18, used average grain diameter be the carbon of 16 μ m in conjunction with particle, and this carbon is to be that the flaky graphite of 2 μ m is made by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 19)
As shown in table 1, in embodiment 19, used average grain diameter be the carbon of 40 μ m in conjunction with particle, and this carbon is to be that the flaky graphite of 16 μ m is made by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 20)
As shown in table 1, in embodiment 20, used average grain diameter be the carbon of 40 μ m in conjunction with particle, and this carbon is to be that the flaky graphite of 18 μ m is made by using average grain diameter in conjunction with particle.At this moment, the amorphous carbon one after another is 20%.
(embodiment 21)
As shown in table 1, in embodiment 21, the battery production method is identical with embodiment 1, has only used Thermocurable plasticization polyvinyl alcohol resin constituent as bond.
(embodiment 22)
As shown in table 1, in embodiment 22, the battery production method is identical with embodiment 9, has only used Thermocurable plasticization polyvinyl alcohol resin constituent as bond.
(comparative example 1)
As shown in table 1, in comparative example 1, having used average grain diameter is that the KMFC of 16 μ m is as carbon material used as anode.Therefore, do not form the foregoing description such by amorphous carbon constitute in conjunction with particle.
(comparative example 2)
As shown in table 1, in comparative example 2, the battery production method is identical with comparative example 1, and only having used average grain diameter is that the flaky graphite of 12 μ m is as carbon material used as anode.
(comparative example 3)
As shown in table 1, in comparative example 3, used average grain diameter be 16 μ m KMFC and by with 1400 ℃ to the two mixture (mixing ratio 80: 20) of petroleum asphalt carries out sintering, the average grain diameter that pulverize to obtain is 20 μ m amorphous carbon as carbon material used as anode.
(comparative example 4)
As shown in table 1, in comparative example 4, having used average grain diameter is that the two mixture (mixing ratio 80: 20) of the KMFC of 16 μ m and the amorphous carbon that average grain diameter is 20 μ m (Wu Yu chemical industry (strain) is made, trade name: カ one ボ ト ロ Application) is as carbon material used as anode.
(comparative example 5)
As shown in table 1, in comparative example 5, used average grain diameter be 12 μ m flaky graphite and with 1400 ℃ to the two mixture (mixing ratio 80: 20) of petroleum asphalt carries out sintering, the average grain diameter that pulverize to obtain is 12 μ m amorphous carbon as carbon material used as anode.
(comparative example 6)
As shown in table 1, in comparative example 6, having used average grain diameter is that the two mixture (mixing ratio 80: 20) of the flaky graphite of 12 μ m and the amorphous carbon that average grain diameter is 12 μ m (Wu Yu chemical industry (strain) is made, trade name: カ one ボ ト ロ Application) is as carbon material used as anode.
＜test and assessment 〉
Then, at the embodiment that makes in a manner described and each battery of comparative example, a series of test below having carried out.
When the room temperature environment temperature is 25 ± 2 ℃, discharge after each battery of embodiment and comparative example charged, measure its discharge capacity.Charge condition is set at: constant voltage 4.2V, restriction electric current 90A, 3.5 hours charging intervals.Discharging condition is set at: constant current 30A, final voltage 2.7V.Each battery of the foregoing description and comparative example can obtain the discharge capacity of about 90Ah degree.And, likening to of first discharge capacity and primary charging capacity is first efficiency for charge-discharge (% of unit).
And, under these conditions, obtain DOD and be at 0% o'clock and DOD is the discharge power of each battery of 80% o'clock.Assay method is as follows: when 10A, 30A and each discharging current of 90A, read the 10th second voltage, on the longitudinal axis, draw the mensuration voltage corresponding then with the transverse axis current value, calculate 3 the link to each other near linear of formation and the current values of 2.7V joining, with amassing of this current value and 2.7V, as power.In addition, to calculate DOD be the power measured in 80% o'clock and DOD is that the percentage of the power of 0% o'clock mensuration represents that DOD is 80% o'clock a power.
And, when 60 ± 2 ℃ of hot environment temperature, each battery to embodiment and comparative example repeats to discharge and recharge after 100 times under these conditions, mensuration discharge capacity and DOD are 0% o'clock power, with this discharge capacity and DOD be 0% o'clock power respectively to the percentage of initial discharge capacity and initial stage power, represented as discharge capacity sustainment rate and power sustainment rate.Certainly, sustainment rate is high more, and life characteristic runs off look.
These mensuration to discharge capacity and power all are to carry out in ambient temperature is 25 ± 2 ℃ atmosphere.[table 2]
As shown in table 2, the battery of embodiment is compared with the battery of comparative example, can obtain high power in the early stage.Wherein, with between the flaky graphite particle with the amorphous carbon combination in conjunction with the battery of particle as the embodiment 9～embodiment 20 of carbon material used as anode, the power of Huo Deing is higher in the early stage.
The amorphous carbon one after another is set at 4～24% scopes interior embodiment 1～3, embodiment 6～11 and the battery of embodiment 14～20, DOD is 80% o'clock power and discharges and recharges 100 discharge capacity sustainment rates after the circulation at high temperature and show as high value in the early stage, in contrast, thereby the amorphous carbon one after another is set to 26% is higher than 24% embodiment 5 and the battery of embodiment 13, and DOD is that 80% o'clock power shows as low value in the early stage.And, be lower than 4% embodiment 4 and the battery of embodiment 12 thereby be set to 3% for the amorphous carbon one after another, discharge and recharge 100 discharge capacity sustainment rates after the circulation at high temperature and show as low value.
Be set at the battery of embodiment 1～5, embodiment 7, embodiment 9～13, embodiment 15 and embodiment 17～20 in 14～40 mu m ranges in conjunction with the average grain diameter of particle, first efficiency for charge-discharge and in the early stage DOD be 0% o'clock power, discharge and recharge 100 power sustainment rates after the circulation at high temperature and all show as high value.In contrast, be higher than the embodiment 6 of 40 μ m and the battery of embodiment 14 thereby average grain diameter is set to 42 μ m, its in the early stage DOD be that 0% o'clock power shows as low value.And, thereby being set to 12 μ m, average grain diameter is lower than the embodiment 8 of 14 μ m and the battery of embodiment 16, discharge and recharge 100 power sustainment rates after the circulation at high temperature and show as low value, and its first discharging efficiency shows as low slightly value.
Formation is set at embodiment 1～17 in 3～16 mu m ranges and the battery of embodiment 19 in conjunction with the average grain diameter of the graphite particle of particle, its first efficiency for charge-discharge and in the early stage DOD be 0% o'clock power and discharge and recharge 100 power sustainment rates after the circulation at high temperature and all show as high value.In contrast, thereby the average grain diameter that constitutes in conjunction with the graphite particle of particle is set to the battery that 18 μ m are higher than the embodiment 20 of 16 μ m, its in the early stage DOD be that 0% o'clock power shows as low value.And, thereby the average grain diameter that constitutes in conjunction with the graphite particle of particle is set to the battery that 2 μ m are lower than the embodiment 18 of 3 μ m, and it discharges and recharges 100 power sustainment rates after the circulation at high temperature and shows as low value, and first efficiency for charge-discharge shows as low slightly value.
Thermocurable plasticization polyvinyl alcohol resin constituent as the embodiment 21 of bond and the battery of embodiment 22, is discharged and recharged 100 power sustainment rates after the circulation at high temperature and shows as high value.
As mentioned above, regardless of DOD, the column lithium ion battery 20 of present embodiment all can obtain stable power.And,,, also can obtain the battery that power descends less, the discharge capacity sustainment rate is high even when then DOD deepens if the amorphous carbon one after another of carbon material used as anode is set in 4～24% the scope.Therefore, by measuring voltage, can easily detect residual capacity.And, if will be set at 14～40 μ m, can obtain then that first efficiency for charge-discharge is good, initial stage power height and the high battery of power sustainment rate in conjunction with the average grain diameter of particle.And, if the average grain diameter of graphite particle is set at 3～16 μ m, can obtain then that first efficiency for charge-discharge is good, initial stage power height and the high battery of power sustainment rate.If Thermocurable plasticization polyvinyl alcohol resin constituent as above-mentioned bond in conjunction with particle, then can be obtained the higher battery of power sustainment rate.
In addition, in the present embodiment, the large secondary battery used to the used for electric vehicle power supply is described, if but but reach more than 10 seconds more than the battery continuous discharge 50W, not limiting battery size and battery capacity of the present invention then confirmed that the present invention to the battery effect performance of the about 15Ah degree of battery capacity significantly.And in the present embodiment, though cylindrical battery has been made example, the present invention is the shape of limiting battery not, and the present invention also can be applicable to rectangle, other polygons or stacked type battery.And the present invention also can be applicable to the shape except that following battery, and promptly in this battery, as mentioned above, positive and negative outside terminal connects battery cover, and positive and negative outside terminal pushes mutually by the axle core in battery case.As an example of this structure, can enumerate and have the battery that cell cover is riveted to the structure of sealing on the bottom tube-like container (jar).
And, the graphite in conjunction with particle of the carbon material used as anode of spendable formation lithium ion battery the item of putting down in writing, is not done any special restriction beyond the present embodiment in following claim scope, for example, can use native graphite, various Delanium materials etc.And the shape of particle of graphite can comprise flakey, spherical, fibrous, bulk etc., has no particular limits, and still, flaky graphite can obtain better effect.
And, in the present embodiment, LiMn2O4 is used as the positive pole of lithium ion battery, and, phosphorus hexafluoride acid lithium is used as electrolyte by being dissolved into the solution for preparing in the mixed solution of being made up of by 1: 1: 1 volume ratio this three of vinyl carbonate, dimethyl carbonate and diethyl carbonate by 1 mol, but, battery of the present invention is not particularly limited, and as electric conducting material and bond, can also use normally used any electric conducting material and bond.And the present invention does not limit the mixing composition of positive-electrode mixture layer and negative pole mixture layer, coating amount, electrode mixture density and the thickness of electrode of mixture.Usually, can synthesize LiMn2O4 by to suitable lithium salts with manganese oxide mixes and sintering, but the rate of charge by control lithium salts and manganese oxide, the Li/Mn that can obtain to expect ratio.
And,, can adopt the material that can insert and break away from lithium as spendable lithium ion battery positive active material beyond present embodiment, preferably use the lithium-manganese composite oxide that inserts the capacity lithium in advance, also can use the LiMn2O4 with spinel structure, perhaps the part of manganese in the crystallization or lithium is with other metals (for example, Li, Fe, Co, Ni, Cr, Al, Mg etc.) material of replacing or mixing up.
And,, can use common lithium salts is dissolved in the organic solvent and the electrolyte of preparation as electrolyte and with its salt as nonaqueous electrolytic solution.But used lithium salts and organic solvent are not particularly limited.For example, as electrolyte, can use LiClO
4, LiAsF
6, LiPF
6, LiBF
4, LiB (C
6H
5)
4, CH
3SO
3Li, CF
3SO
3Li etc. or its mixture.As the nonaqueous electrolytic solution organic solvent, can use trimethylene carbonic ester, vinyl carbonate, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, gamma-butyrolacton, oxolane, 1,3-dioxolanes, 4-methyl isophthalic acid, 3 dioxolanes, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile etc., perhaps its two or more mixed solvent, and also be not particularly limited mixing mix proportion.And, use beyond the above-mentioned electrolyte, lithium salts disperseed and be dissolved in polyelectrolyte in the polymer body, also can obtain effect of the present invention.
And, comprise with the plate active material bond as spendable lithium ion battery beyond present embodiment: polytetrafluoroethylene, polyethylene, polystyrene, polybutadiene, buttress rubber, acrylonitrile-butadiene rubber; butadiene-styrene rubber; polysulfide rubber; celluloid; cyanethyl cellulose; various latex; acrylonitrile; PVF; 1; 1-difluoroethylene; fluorine propylene; polymer such as fluorine chlorobutadiene and composition thereof etc.; still; as described in present embodiment; if use Thermocurable plasticization polyvinyl alcohol resin constituent;, also can obtain the high battery of power sustainment rate even then after repeating the high temperature charge and discharge cycles.
And, in the present embodiment, although to using by base material as polyimides, the adhesive tape made by the hexamethyl acrylate of coating is described as insulation-coated example on its one side, but, also can suitably use, for example, base material is polyolefin such as polypropylene, polyethylene, coating is by the adhesive tape of acryloid cements such as hexamethyl acrylate, butyl acrylate on its one or both sides, the band of being made up of polyolefin or polyimides etc. of applying adhesive not above perhaps also can using.
Claims (10)
1. nonaqueous electrolytic solution secondary battery, wherein, the electrode group is soaked in nonaqueous electrolytic solution and is contained in the battery case, and positive pole and negative pole in this electrode group dispose by separator, wherein, described positive pole is used as positive active material with complex Li-Mn-oxide, and described negative pole is used as the negative pole bond with material with carbon element as negative electrode active material and with resin combination, but and reach more than 10 seconds more than this battery continuous discharge 50W, it is characterized in that, above-mentioned material with carbon element be between graphite particle with the amorphous carbon combination in conjunction with particle.
2. nonaqueous electrolytic solution secondary battery according to claim 1 is characterized in that, above-mentioned graphite particle is the flaky graphite particle.
3. nonaqueous electrolytic solution secondary battery according to claim 1 and 2 is characterized in that, above-mentioned ratio in conjunction with the above-mentioned amorphous carbon in the particle is that the above-mentioned relatively quality in conjunction with particle is 4%～24%.
4. according to any one described nonaqueous electrolytic solution secondary battery in the claim 1 to 3, it is characterized in that above-mentioned average grain diameter in conjunction with particle is 14 μ m～40 μ m.
5. according to any one described nonaqueous electrolytic solution secondary battery in the claim 1 to 4, it is characterized in that the average grain diameter of above-mentioned graphite particle is 3 μ m～16 μ m.
6. according to any one described nonaqueous electrolytic solution secondary battery in the claim 1 to 5, it is characterized in that above-mentioned resin combination is the Thermocurable plasticization polyvinyl alcohol resin based on the sex change of polyvinyl alcohol.
7. nonaqueous electrolytic solution secondary battery according to claim 6 is characterized in that, above-mentioned resin combination comprises: first resinous principle of being made up of the Thermocurable polyvinyl alcohol resin; And second resinous principle of forming by the acrylic resin plasticizer.
8. nonaqueous electrolytic solution secondary battery according to claim 7 is characterized in that, above-mentioned first resinous principle is to make the polyvinyl alcohol resin of average degree of polymerization about 2000 and the Thermocurable polyvinyl alcohol resin of cyclic acid anhydride reaction.
9. according to claim 7 or 8 described nonaqueous electrolytic solution secondary batteries, it is characterized in that above-mentioned second resinous principle is the acrylic resin plasticizer that makes lauryl acrylate/acrylic copolymer and the reaction of difunctionality type epoxy resin.
10. according to any one described nonaqueous electrolytic solution secondary battery in the claim 1 to 9, it is characterized in that battery capacity is more than the 15Ah.
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| CNB021264686A CN1228880C (en) | 2002-07-22 | 2002-07-22 | Non-aqueous electrolytic solution secondary cell |
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| CNB021264686A CN1228880C (en) | 2002-07-22 | 2002-07-22 | Non-aqueous electrolytic solution secondary cell |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907848B (en) * | 2005-08-04 | 2010-11-10 | 中央电气工业株式会社 | Carbon powder for use in cathode materials of non-aqueous secondary battery |
| CN102456915A (en) * | 2010-10-26 | 2012-05-16 | 通用汽车环球科技运作有限责任公司 | Electrolytic cell and method of estimating a state of charge thereof |
| CN102610791A (en) * | 2012-02-27 | 2012-07-25 | 宁德新能源科技有限公司 | Lithium ion battery for plug-in type hybrid power automobile and cathode thereof |
| CN103378357A (en) * | 2012-04-30 | 2013-10-30 | 三星Sdi株式会社 | Negative electrode composition for rechargeable lithium battery, negative electrode comprising same and rechargeable lithium battery comprising same |
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2002
- 2002-07-22 CN CNB021264686A patent/CN1228880C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907848B (en) * | 2005-08-04 | 2010-11-10 | 中央电气工业株式会社 | Carbon powder for use in cathode materials of non-aqueous secondary battery |
| CN102456915A (en) * | 2010-10-26 | 2012-05-16 | 通用汽车环球科技运作有限责任公司 | Electrolytic cell and method of estimating a state of charge thereof |
| CN102610791A (en) * | 2012-02-27 | 2012-07-25 | 宁德新能源科技有限公司 | Lithium ion battery for plug-in type hybrid power automobile and cathode thereof |
| CN103378357A (en) * | 2012-04-30 | 2013-10-30 | 三星Sdi株式会社 | Negative electrode composition for rechargeable lithium battery, negative electrode comprising same and rechargeable lithium battery comprising same |
| US9508982B2 (en) | 2012-04-30 | 2016-11-29 | Samsung Sdi Co., Ltd. | Negative electrode composition for rechargeable lithium battery, negative electrode comprising same and rechargeable lithium battery comprising same |
| CN103378357B (en) * | 2012-04-30 | 2017-08-01 | 三星Sdi株式会社 | Negative electrode compositions, negative electrode and lithium rechargeable battery |
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| Publication number | Publication date |
|---|---|
| CN1228880C (en) | 2005-11-23 |
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