CN103035938B - Secondary battery - Google Patents
Secondary battery Download PDFInfo
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- CN103035938B CN103035938B CN201210320797.4A CN201210320797A CN103035938B CN 103035938 B CN103035938 B CN 103035938B CN 201210320797 A CN201210320797 A CN 201210320797A CN 103035938 B CN103035938 B CN 103035938B
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- active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
The invention relates to a secondary battery capable of effectively charging and discharging. The secondary battery comprises an anode having positive active materials, a cathode having negative active materials, and electrolyte. The positive active materials contain first active substance particles and second active substance particles which have charging potential and average particle diameter different from those of the negative active materials.
Description
Technical field
The present invention relates to a kind of secondary cell.
Background technology
In recent years, the motor vehicle such as electric automobile and plug-in hybrid-power automobile is by practical in a large number.The driving battery that such motor vehicle carries have employed the secondary cell that can charge.
In the secondary battery, as negative electrode active material, such as, use graphite, as positive active material, use and can inhale the metal oxide storing and discharge lithium.Metal oxide as positive active material is mainly present in positive electrode active material layer with particle shape.In this case, there will be a known that fail safe when can realize overcharge is high, initial capacity large, employ the lithium ion battery (for example, referring to patent documentation 1) of the different multiple anode active substances material of domain size distribution.
Patent documentation 1: Japanese Unexamined Patent Publication 2010-176996 publication (claim 1, summary etc.)
Summary of the invention
The problem that invention will solve
Although fail safe during above-mentioned lithium ion battery overcharge is high, initial capacity is large, when being equipped on electric automobile etc., create following problem.Such as, during charging rapidly under the situation such as regenerative braking when descending or in travelling during emergency brake, although compared with when charging normal, in secondary cell, flow into excessive charging current, but because the charging response of secondary cell is lower, therefore there is the problem that can not efficiently charge.It should be noted that, when such problem not only appears at and charges rapidly, be also same when when the flash of light of secondary cell being such as equipped on camera etc. during sudden discharge.
Therefore, problem of the present invention is the problem for solving above-mentioned prior art, and provides a kind of secondary cell of discharge and recharge when efficiently can carry out discharge and recharge rapidly.
Solve the means of problem
Secondary cell of the present invention possesses: the positive pole containing positive active material, negative pole containing negative electrode active material and electrolyte, it is characterized in that, above-mentioned positive active material is at least containing and average grain diameter mutually different 1st active material particle and 2nd active material particle different relative to the charging potential of above-mentioned negative electrode active material.Due to and average grain diameter mutually different 1st active material particle and 2nd active material particle different containing charging potential, therefore, it is possible to improve discharge and recharge response, realize efficiently discharge and recharge during discharge and recharge rapidly.
Above-mentioned 2nd active material particle of above-mentioned positive active material is preferably average grain diameter and is less than above-mentioned 1st active material particle, and, relative to the charging potential of above-mentioned negative electrode active material higher than the particle of above-mentioned 1st active material particle.By formation like this, charging response can be improved further, realize charging when charging rapidly efficiently.
Above-mentioned positive pole preferably comprises collector foil and is formed at the positive electrode active material layer of above-mentioned collector foil also containing above-mentioned positive active material, this positive electrode active material layer is preferably along with towards above-mentioned collector foil side, and above-mentioned 1st active material particle becomes more than above-mentioned 2nd active material particle.By formation like this, charging response can be improved, realize charging when charging rapidly efficiently.
The average grain diameter of above-mentioned 1st active material particle is preferably 1 ~ 50 μm, and the average grain diameter of above-mentioned 2nd active material particle is preferably 20nm ~ 1 μm.Because being such scope, so easily slurry can be formed when manufacturing, and discharge and recharge when can realize efficient discharge and recharge rapidly.
Invention effect
According to secondary cell of the present invention, when can realize discharge and recharge rapidly, efficiently carry out the excellent effect of discharge and recharge.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the vehicle for illustration of the secondary cell being equipped with present embodiment.
Fig. 2 is the schematic diagram of the secondary cell for illustration of present embodiment.
Fig. 3 is (1) schematic diagram, (2) partial enlarged drawing of the electrode structure for illustration of present embodiment.
Fig. 4 is the schematic diagram of lithium ion mobility when discharging for illustration of present embodiment.
Fig. 5 is the schematic diagram of lithium ion mobility when discharging for illustration of present embodiment.
Fig. 6 is the schematic diagram of lithium ion mobility when charging for illustration of present embodiment.
Fig. 7 is the schematic diagram for illustration of lithium ion mobility when charging rapidly in prior art.
Fig. 8 is the schematic diagram for illustration of lithium ion mobility during the charging rapidly of present embodiment.
Symbol description
1: vehicle
2: secondary cell
3: battery component
11: battery case
12: electrode section
13: insulation board
14: electrolyte
15: cap
16: negative tab
17: positive tab
18: negative terminal
19: positive terminal
21: spacer
22: positive pole
23: negative pole
24: positive pole collector foil
25: positive electrode active material layer
26: negative pole collector foil
27: negative electrode active material layer
30: lithium ion
31: the 1 active material particles
32: the 2 active material particles
33: negative electrode active material
Embodiment
With accompanying drawing, embodiments of the present invention are described.
Vehicle 1 is electric automobile.The vehicle battery assembly 3 being equipped with multiple secondary cell 2 is equipped on the bottom (under base plate) of the vehicles 1 such as such as electric automobile.By the supply such as the traveling motor electric power of each secondary cell 2 to vehicle 1.
By the following drawings, secondary cell 2 is described.
As shown in Figure 2, secondary cell 2 has battery case 11.Electrode section 12 to be incorporated in battery case 11 and to insulate by insulation board 13 and battery case 11.Be full of electrolyte 14 in battery case 11, battery case 11 is sealed by cap 15.
Electrode section 12 is provided with negative tab 16 and positive tab 17, and it is connected to anode member and the positive pole parts of electrode section 12 described later.Negative tab 16 is connected with the negative terminal 18 being arranged at cap 15, and positive tab 17 is connected with the positive terminal 19 being arranged at cap 15.
As shown in Figure 3, electrode section 12 is reeled by battery lead plate and is formed, and this battery lead plate to be separated by spacer 21 and the positive pole 22 that arranges and negative pole 23 form.Positive pole 22 has positive pole collector foil 24 and is arranged on the two sides of positive pole collector foil 24 and the positive electrode active material layer 25 containing positive active material.Negative pole 23 has negative pole collector foil 26 and is arranged on the two sides of negative pole collector foil 26 and the negative electrode active material layer 27 containing negative electrode active material.
Granular 1st active material particle as positive active material and the 2nd active material particle is contained in the positive electrode active material layer 25 of the positive pole 22 of electrode section 12.The charging potential relative to negative electrode active material of the 2nd active material particle is higher than the 1st active material particle, that is, the adsorption capacity of its lithium ion is higher than the 1st active material particle, and its average grain diameter is less than the 1st active material particle.It should be noted that, charging potential is low, and to be also referred to as electronegativity low.
In the present embodiment, positive active material is not formed separately with the 1st active material particle usually used, and high for lithium ion adsorption capacity and that particle diameter is little the 2nd active material particle is further used as positive active material mixes, the secondary cell that when forming charging rapidly, charging response is high.Below this point is described.
First be described with during the conventional discharge of Fig. 4 and Fig. 5 to present embodiment.In Fig. 4, graphical representation is relative to SOC(charged state) cell voltage, the schematic diagram of the positive pole during SOC represented with zero and the state of negative pole also illustrates simultaneously.
First, as shown in the curve chart of Fig. 4, the secondary cell of present embodiment is with under the state that is SOC80% of the voltage relative to SOC, and the mode that the cell voltage of secondary cell raises gradually changes.This is the cause of the 2nd active material particle 32 high containing lithium ion adsorption capacity in positive active material.Namely, in the secondary cell of present embodiment, as positive active material, according to SOC benchmark, by the 2nd active material particle 32 and the 1st active material particle 31 with relative to 80% of the 1st active material particle 31, make the 2nd active material particle 32 be 20% ratio mix.
Fig. 4 (1) represents fully charged state.That is, in positive pole, lithium ion 30 is not stored in the 1st active material particle 31 and the 2nd active material particle 32 by suction, and all lithium ions 30 are all received in negative electrode active material 33.After electric discharge starts, release lithium ion 30 from negative electrode active material 33, lithium ion 30 moves in positive active material.In the case, first lithium ion 30 is inhaled by the 2nd active material particle 32 that lithium ion adsorption capacity in positive active material is large and is stored.
As shown in Fig. 4 (2), along with the carrying out of electric discharge, when the SOC of secondary cell reaches 80%, can not inhale in the 2nd active material particle 32 and store more lithium ion 30.After the 2nd active material particle 32 such as shown in this Fig. 4 (2) reaches the state can not taking in lithium ion 30, as shown in Fig. 5 (1), lithium ion 30 is stored in the 1st active material particle 31 by suction.So as shown in Fig. 5 (2), electric discharge afterwards proceeds, the 1st active material particle 31 is also inhaled completely and has been stored lithium ion 30, becomes the state (complete discharge condition) that all lithium ions 30 depart from from negative pole.
That is, in the secondary cell of present embodiment, during electric discharge, when SOC is 100 ~ 80%, lithium ion 30 is stored in the 2nd active material particle 32 by suction, SOC be lower than 80% ~ 0% time, lithium ion 30 is stored in the 1st active material particle 31 by suction.
Then, with Fig. 6, charging normal from this complete discharge condition is described.
As shown in Fig. 6 (1), from complete discharge condition after charging, because the lithium ion adsorption capacity of the 2nd active material particle 32 is high, first lithium ion 30 departs from and goes from the 1st active material particle 31.As shown in Fig. 6 (2), after lithium ion 30 departs from from the 1st all active material particles 31, next, lithium ion 30 also starts to depart from from the 2nd active material particle 32.So, as shown in Fig. 6 (3), after lithium ion 30 departs from from the 2nd all active material particles 32, become fully charged state.
That is, in the secondary cell of present embodiment, during charging, SOC is 0 ~ lower than 80% time, lithium ion 30 is discharged by from the 1st active material particle 31, and when SOC is 80 ~ 100%, lithium ion 30 is discharged by from the 2nd active material particle 32.
Like this, when charging normal, lithium ion easily discharges from low the 1st active material particle 31 of lithium ion adsorption capacity, and lithium ion is not easy to discharge from high the 2nd active material particle 32 of lithium ion adsorption capacity.
In contrast, when charging rapidly, different from when charging normal, such as can because of regenerative braking at short notice, make the charging current be greater than when charging normal flow into secondary cell.Be described when this being charged rapidly with Fig. 7,8.
Fig. 7 be for illustration of such as prior art there is a kind of active material particle when charge rapidly time (1) curve chart and (2) schematic diagram.Graphical representation is relative to the charging voltage of charging current.Charging current value in curve chart is I
1time, positive pole and negative pole are the state in Fig. 7 (2).
When charging normal, (in curve chart, charging current is I
1time), as mentioned above, inhale the lithium ion 30 stored in the 1st active material particle 31 and be released.But in the case, because the surface area of the per unit volume of the 1st active material particle 31 is less, lithium ion 30 is difficult to release, and therefore, impedance increases, and charging voltage easily rises.
And (in curve chart, charging current value is I when creating very large charging current because of regenerative braking
2time), because charging current is very large, so, and if I
1when represented state is same resistance value, charging voltage will become also higher than upper voltage limit, can not charge.
On the other hand, in the present embodiment, described in following Fig. 8, owing to not only having the 1st active material particle 31, but also there is the 2nd active material particle 32, therefore, charging response is high, further, because charging voltage is difficult to become higher than upper voltage limit, so can high efficiency charge when charging rapidly.
Fig. 8 is for illustration of (1) curve chart when charging rapidly when present embodiment and (2), (3) schematic diagram.Graphical representation is relative to the charging voltage of charging current.Charging current in curve chart is I
1, I
2time, positive pole and negative pole are respectively the state in Fig. 8 (2), (3).
(I when charging normal
1situation), as mentioned above, discharge lithium ion 30 from the 1st active material particle 31.But in the case, because the surface area of the per unit volume of the 1st active material particle 31 is little, lithium ion 30 is difficult to release, therefore, impedance increases, and charging voltage easily rises.In addition, because the lithium ion adsorption capacity of the 2nd active material particle 32 is higher, be therefore difficult to discharge lithium ion.
And, because of (I when regenerative braking etc. charges rapidly
2situation), flow through very large charging current.In the case, once produce high voltage because very large charging current flows into secondary cell, although the surface area of per unit volume is comparatively large, lithium ion 30 can become the 2nd active material particle 32 be easy to from being usually difficult to discharge lithium ion 30 and discharge.That is, the surface area due to the per unit volume of the 2nd active material particle 32 is comparatively large, therefore, being applied with in high-tension situation, easily discharges lithium ion.
Like this, with release the situation of lithium ion from the 1st active material particle 31 compared with, impedance step-down.Consequently, as cell integrated, relative to charging current, voltage is difficult to rise.Therefore, when charging rapidly, upper voltage limit becomes and is difficult to exceed, and can charge expeditiously when thus charging rapidly.
And, because the recovery time is elongated, namely the charging interval is elongated rapidly, even if therefore in the 2nd active material particle 32, all lithium ions are all released, compared with the 1st active material particle 31, the lithium ion adsorption capacity of the 2nd active material particle is also very high, so lithium ion existing in the 1st active material particle 31 will move to the 2nd active material particle 32.Thus, again discharge lithium ion from the 2nd active material particle 32 at once, thus charging current when can receive regeneration expeditiously and charging.
So, in the present embodiment, define not only the 1st active material particle 31, and the 2nd little for average grain diameter active material particle 32 is also mixed as positive active material, thus can receive excessive charging current when charging rapidly expeditiously and charge.In the case, because the lithium ion adsorption capacity of the 2nd active material particle 32 is higher, almost in all cases, lithium ion all will be stored in the 2nd active material particle 32 by suction, no matter start to charge rapidly with which in moment, charging current when all efficiently can receive regeneration at once and charging.And, even if do not inhale when storing lithium ion in the 2nd active material particle 32, because lithium ion moves to the 2nd active material particle 32 from the 1st active material particle 31, can charge rapidly expeditiously equally.
In the present embodiment, owing to being also mixed with 2nd active material of lithium ion adsorption capacity higher than the 1st active material, and only formed compared with the situation of active material layer by the 1st active material, the electromotive force of battery can be improved.Now, if similarly all active material layers are only made up of the 2nd active material, because the low problem of response when charging rapidly can be produced, so be not preferred.
In addition, if make the particle diameter of all positive active material particles all very little (such as about 0.1 μm), be then difficult in a manufacturing process form slurry.But, in the present embodiment, due to the 1st active material particle 31 is mixed with the 2nd active material particle 32, therefore make slurry be formed and be easier to.
Namely, as mentioned above, owing to comprising the 1st active material particle 31 and the 2nd active material particle 32 in present embodiment, thus the charging response that improve when charging rapidly, and, in the present embodiment, due in positive electrode active material layer using the 1st active material particle 31 as the main active material of positive pole, and containing the 2nd active material particle 32, therefore improve the electromotive force of battery, thus improve the voltage characteristic of battery.In addition, owing to not only having the 2nd active material particle 32, also have the 1st active material particle 31, therefore, slurry when manufacturing easily is formed.
As such positive active material, active material used can be enumerated usually, such as can inhale the metal oxide storing and release lithium ion, as layer structure type metal oxide, spinel-type metal oxide and metallic compound, oxidizing acid salt form metal oxide etc.As layer structure type metal oxide, lithium-nickel-based compound oxide, lithium-cobalt system composite oxides, ternary system composite oxides (LiCo1/3Ni1/3Mn1/3O2) can be enumerated.As lithium-nickel-based compound oxide, lithium nickelate (LiNiO2) preferably can be enumerated.As lithium-cobalt system composite oxides, cobalt acid lithium (LiCoO2) preferably can be enumerated.As spinel-type metal oxide, the lithium manganese system complex oxides such as LiMn2O4 (LiMn2O4) preferably can be enumerated.As oxidizing acid salt form metal oxide, LiFePO4 (LiFePO4), lithium manganese phosphate (LiMnPO4), silicon phosphate lithium etc. can be enumerated.
Thus, as mentioned above, select the 2nd active material and the 1st active material, make the lithium ion adsorption capacity of the 1st active material particle 31 lower than the 2nd active material particle 32.In the case, the difference of lithium ion adsorption capacity, namely charged electrical potential difference is preferably 0.2 ~ 1.0V.If charged electrical potential difference is lower than 0.2V, be then difficult to the advantage realizing using two kinds of different active materials to bring, and if potential difference is greater than 1.0V, then the charging performance decline of battery.Therefore, be preferably within this scope.
Further, as mentioned above, because the 2nd active material particle 32 receives charging current when charging rapidly, be therefore preferably the capacity benchmark according to battery, the 2nd active material particle 32 content comprised is 1 ~ 20%.Because being included within the scope of this, just such as regenerative braking can be made and the charging current that produces is charged expeditiously.Be more preferably the 2nd active material particle 32 containing 2 ~ 10% according to the capacity benchmark of battery.
As the combination of the 2nd such active material and the 1st active material, can enumerate: such as use LiMn2O4 (charging potential when lithium metal being used in negative pole is 4.1V) as the 2nd active material, use lithium nickelate (charging potential when lithium metal being used in negative pole is 3.6V) and/or cobalt acid lithium (charging potential when lithium metal being used in negative pole is 3.8V) as the 1st active material.
It is little as far as possible that the 2nd active material particle 32 is like this preferably average grain diameter, but for being easy to form slurry, preferred average grain diameter (d(50)) be 20nm ~ 1 μm, be more preferably 50 ~ 500nm.The average grain diameter of the 1st active material particle 31 is 1 ~ 50 μm, is more preferably 2 ~ 20 μm.It should be noted that, average grain diameter described herein refers to the particle diameter value (d(50) of the integrating point rate 50% of volume reference).As the assay method of average grain diameter, such as, laser diffractometry or scattering method etc. can be adopted.Because the 1st active material particle 31 and the 2nd active material particle 32 are within the scope of this respectively, therefore, it is possible to easily form slurry, and charging current can be charged expeditiously.
As above-mentioned negative electrode active material, active material used can be enumerated usually, the carbonaceous materials such as such as lithium metal, lithium alloy, metal oxide, metal sulfide, metal nitride and graphite.As metal oxide, can enumerate: such as tin-oxide, Si oxide etc. have the material of irreversibility capacity.As the graphite of carbonaceous material, can be Delanium also can be native graphite, in the present embodiment, use graphite as negative electrode active material.
As adhesive, adhesive used can be adopted usually, such as, can use Kynoar.In addition, can also containing conductivity enhancer, electrolyte (such as lithium salts (support electrolyte matter), ion-conducting polymers etc.) such as acetylene blacks in active material layer.In addition, when containing ion-conducting polymers, can also containing the polymerization initiator for making above-mentioned polymer polymerizing.
In addition, as negative pole collector foil 26, such as, can use aluminium or copper.
As electrolyte, electrolyte used can be enumerated usually, such as ethylene carbonate or the propylene carbonate of cyclic carbonate, or, be dissolved with the LiPF of about 1 molar concentration in the mixed solution as the diethyl carbonate of linear carbonate, methyl ethyl carbonate, diethyl carbonate
6organic electrolyte.
In the present embodiment, by making positive electrode active material layer contain high and the 2nd active material that particle diameter is little of charging potential and improve the charging response under charging rapidly, but this is not limited to.Such as, also can arrange there is the high and positive electrode active material layer of the active material that particle diameter is large of the low and active material that particle diameter is little of the low i.e. lithium ion adsorption capacity of charging potential and charging potential height and lithium ion adsorption capacity.In this case, better to the response of discharging current during sudden discharge.That is, during sudden discharge, because easily receive lithium ion in the little material of particle diameter, so, can discharging current be received expeditiously and discharge, the secondary cell that when can form electric discharge, response is high.
In addition, as in the embodiment described in, main with lithium ion adsorption capacity the high and active material that particle diameter is little and lithium ion adsorption capacity low and in the positive active material of the active material that particle diameter is large these two kinds composition, can also low containing lithium ion the adsorption capacity again and active material that particle diameter is little and the high and active material that particle diameter is large of lithium ion adsorption capacity.In this case, also can improve any one response in charging current during discharge and recharge rapidly and discharging current.
The manufacture method of the electrode section of the secondary cell of present embodiment is below described.
The electrode of electrode section is formed by slurry formation process and coating drying process.
By mixing such as electric conducting materials, then mixed dispersion liquid, after making its drying, obtain composite conducting material powder.Then, mixed cathode active material and adhesive in obtained composite conducting material powder, mixing makes it reach required solids content, thus obtains slurry (slurry formation process).Then, collector foil applies gained slurry, make it dry and form electrode layer (coating drying process).By each for gained polar stack in spacer, thus form battery lead plate.Finally, this laminated sheet is reeled along its length, make electrode section.
When forming electrode layer, for improving the current collection performance of electrode layer, the different slurry of the 2nd active material concentration can be formed to form each layer.Particularly positive electrode active material layer, is preferably to make the 1st active material particle 31 be formed more than the mode of the 2nd active material particle 32 towards collector foil side.If form electrode layer like this, just current collection performance can be improved further.
Below, by embodiment, the present invention is further described.
Embodiment
As embodiment 1, making secondary cell as described below.Mix containing the combined conductive agent powder as the acetylene black of electric conducting material, the lithium nickelate powder as the 1st positive active material (average grain diameter 5 μm) and the LiMn2O4 powder (average grain diameter 0.2 μm) as the 2nd positive active material, make according to SOC benchmark, the 2nd positive active material reaches 2% of battery capacity.Mix the Kynoar as adhesive again, modulation anode active material slurry.Obtained anode active material slurry be coated in the two sides of aluminum collector foil and make it dry, thus forming positive pole.
In addition, the negative electrode active material slurry of modulation containing graphite.Said composition be coated in the two sides of copper collector foil and make it dry, thus forming negative pole.
The positive pole obtained carries out lamination with negative pole together with the spacer be made up of porous polyethylene sheet material, is reeled along its length by this laminated sheet, forms electrode section.This electrode section is housed in exterior package container together with the ethylene carbonate as nonaqueous electrolyte, is made into secondary cell.
As embodiment 2, be replaced by cobalt acid lithium (average grain diameter 0.2 μm) LiMn2O4 to be used as the 2nd active material particle 32 to mix, make according to SOC benchmark, the 2nd positive active material reaches 10% of battery capacity.
As comparative example, except there is no the 2nd active material particle 32, under identical condition, make secondary cell.
When the electric automobile that is 1000kg with 30 meters of vehicle weights travelled per second with 0.5G bring to a halt stop time, to stopping, needed for 6 seconds.Now, the power budget that regenerative braking produces is for being 150kW to the maximum, and electric energy is estimated as 450kJ(=125Wh).It should be noted that, charge power when charging rapidly because common is below 50kW, so, more than 3 times of the charge power when power making battery component receive because of regenerative braking is routine.
To the secondary cell that makes in each secondary cell made in embodiment 1,2 and comparative example, the charging of the power electric energy charged to each battery when having carried out being equivalent to have carried out the charging of 150kW, 125Wh to entire vehicle (i.e. battery component entirety).Charge in each secondary cell of embodiment 1,2 gained, but in the secondary cell of comparative example gained, midway exceedes the upper voltage limit (overvoltage) of battery, failed to realize charging.It should be noted that, in common electric automobile, because about 100 secondary cells form a battery component, the electric energy that therefore each battery is received is about 1/100 of entire vehicle.
From these embodiments and comparative example, owing to not only having the 1st active material particle 31, also have average grain diameter be less than the 1st active material particle 31 and lithium ion adsorption capacity higher than the 2nd active material particle 32 of the 1st active material particle, thus also when charging rapidly can efficiently receive charging current and charge.
In the present embodiment, secondary cell is that electric automobile is used, but is not limited to this.Also can be used for motor vehicle, such as, also may be used for hybrid electric vehicle.When for hybrid electric vehicle, preferably containing the 2nd active material particle 32 with the capacity benchmark of battery being 1 ~ 30%.Be more preferably 5 ~ 25%.By content within the scope of this, the charging of produced charging current of also can efficiently charging rapidly in hybrid vehicle.
Secondary cell of the present invention can charge expeditiously when charging rapidly.This secondary cell, such as, because can be mounted on a vehicle, so, can be used for vehicle manufacturing industry field.
Claims (5)
1. a secondary cell, it possesses: the positive pole containing positive active material, negative pole containing negative electrode active material and electrolyte, is characterized in that,
Described positive active material at least containing and average grain diameter mutually different 1st active material particle and 2nd active material particle different relative to the charging potential of described negative electrode active material,
The average grain diameter of described 2nd active material particle of described positive active material is less than described 1st active material particle, and, the charging potential relative to described negative electrode active material of described 2nd active material particle higher than described 1st active material particle,
Described just having collector foil and be formed at the positive electrode active material layer of described collector foil also containing described positive active material, described positive electrode active material layer is along with towards described collector foil side, and described 1st active material particle becomes more than described 2nd active material particle.
2. secondary cell according to claim 1, is characterized in that,
The average grain diameter of described 1st active material particle is 1 ~ 50 μm, and the average grain diameter of described 2nd active material particle is 20nm ~ 1 μm.
3. secondary cell according to claim 1, is characterized in that,
The adsorption capacity of the lithium ion of described 2nd active material particle is higher than the adsorption capacity of the lithium ion of described 1st active material particle.
4. secondary cell according to claim 1, is characterized in that,
Described positive active material contains as the lithium nickelate powder of described 1st active material particle and the LiMn2O4 powder as described 2nd active material particle, and according to SOC benchmark with described 2nd active material particle be battery capacity 2% mode mix.
5. secondary cell according to claim 1, is characterized in that,
Described positive active material contains the lithium nickelate powder as described 1st active material particle and the acid of the cobalt as described 2nd active material particle lithium powder, and according to SOC benchmark with described 2nd active material particle be battery capacity 10% mode mix.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-212724 | 2011-09-28 | ||
| JP2011212724A JP5696850B2 (en) | 2011-09-28 | 2011-09-28 | Secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103035938A CN103035938A (en) | 2013-04-10 |
| CN103035938B true CN103035938B (en) | 2015-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201210320797.4A Expired - Fee Related CN103035938B (en) | 2011-09-28 | 2012-08-31 | Secondary battery |
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| JP (1) | JP5696850B2 (en) |
| KR (1) | KR101457267B1 (en) |
| CN (1) | CN103035938B (en) |
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| JP6235251B2 (en) * | 2013-06-28 | 2017-11-22 | 日立オートモティブシステムズ株式会社 | Secondary battery system |
| JP6896783B2 (en) * | 2019-03-11 | 2021-06-30 | 株式会社東芝 | Rechargeable battery system, rechargeable battery, and assembled battery system |
| JPWO2022059336A1 (en) * | 2020-09-18 | 2022-03-24 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128949A (en) * | 2005-02-23 | 2008-02-20 | 株式会社Lg化学 | Secondary battery of improved lithium ion mobility and cell capacity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002015726A (en) * | 2000-06-29 | 2002-01-18 | Sony Corp | Gel electrolyte secondary battery |
| JP2007042295A (en) * | 2005-07-29 | 2007-02-15 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JP5103857B2 (en) * | 2005-11-10 | 2012-12-19 | 日産自動車株式会社 | Secondary battery electrode and secondary battery using the same |
| JP5250948B2 (en) * | 2006-07-28 | 2013-07-31 | 株式会社Ｇｓユアサ | Nonaqueous electrolyte secondary battery |
| CN101595582B (en) * | 2007-01-18 | 2015-03-25 | 株式会社Lg化学 | Cathode active material and secondary battery comprising the same |
| JP5150966B2 (en) * | 2007-05-28 | 2013-02-27 | Ｎｅｃエナジーデバイス株式会社 | Non-aqueous electrolyte secondary battery positive electrode and non-aqueous electrolyte secondary battery using the same |
| JP2009026599A (en) * | 2007-07-19 | 2009-02-05 | Toyota Motor Corp | Positive electrode plate, lithium-ion secondary battery, vehicle, and battery loading device |
| JP5549202B2 (en) | 2009-12-01 | 2014-07-16 | セイコーエプソン株式会社 | Optical position detection device, hand device, and display device with position detection function |
| JP2011171150A (en) * | 2010-02-19 | 2011-09-01 | Sony Corp | Positive electrode active material, positive electrode, and nonaqueous electrolyte secondary battery |
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2011
- 2011-09-28 JP JP2011212724A patent/JP5696850B2/en not_active Expired - Fee Related
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2012
- 2012-08-30 KR KR1020120095421A patent/KR101457267B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101128949A (en) * | 2005-02-23 | 2008-02-20 | 株式会社Lg化学 | Secondary battery of improved lithium ion mobility and cell capacity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013073823A (en) | 2013-04-22 |
| CN103035938A (en) | 2013-04-10 |
| JP5696850B2 (en) | 2015-04-08 |
| KR20130034584A (en) | 2013-04-05 |
| KR101457267B1 (en) | 2014-10-31 |
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Address after: No. 21, No. 3, Dingmu, No. 1, Toshiba, Tokyo, Japan Patentee after: Mitsubishi Jidosha Kogyo Kabushiki Kaisha Address before: Tokyo, Japan Patentee before: Mitsubishi Jidosha Kogyo Kabushiki Kaisha |
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