CN102208596B - Secondary battery electrode, preparation method thereof, and secondary battery - Google Patents
Secondary battery electrode, preparation method thereof, and secondary battery Download PDFInfo
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- CN102208596B CN102208596B CN201010141315.XA CN201010141315A CN102208596B CN 102208596 B CN102208596 B CN 102208596B CN 201010141315 A CN201010141315 A CN 201010141315A CN 102208596 B CN102208596 B CN 102208596B
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Abstract
The invention which belongs to the field of secondary batteries provides a current collector and an electrode material which is coated on or filled in the current collector. The electrode material which comprises an electrode active material, an electrode additive, a conductive agent and a binder is characterized in that: the electrode additive is at least one of amorphous carbon loaded VIB, VIIB or VIII family metals; and the electrode additive accounts for no more than 10 wt% of the electrode active material of a secondary battery. The secondary battery provided by the present invention allows a technical problem that the low temperature discharge rate of the secondary battery and the internal resistance of the battery can not be simultaneously improved to be well solved, so the 3C discharge rate of the secondary battery can be averagely increased by at least 3% at a temperature of 10 DEG C below zero, and simultaneously the internal resistance of the battery is reduced by at least 0.02 milliohm.
Description
Technical field
The invention belongs to secondary cell field, the secondary cell particularly relating to a kind of electrode for secondary battery, its preparation method and make with this electrode.
Background technology
The charging-discharging performances of secondary cell (such as Ni-MH battery, nickel-cadmium cell, lithium ion battery), especially discharge rate temperature influence is remarkable.At present, a kind of method improving secondary cell low temperature discharge rate of prior art is blended in other electrode materials (comprising electrode active material, binding agent, conductive agent etc.) by amorphous carbon material (such as carbon fiber, amorphous carbon, vitreous carbon, carbon aerogels etc.) larger for surface energy to be coated on negative or positive electrode.Although the low temperature discharge rate of this method to secondary cell has certain improvement, because the conductivity of amorphous carbon is poor, thus the internal resistance of cell is increased, namely the low temperature discharge rate of battery and internal resistance are difficult to improve simultaneously.
Summary of the invention
In order to the low temperature discharge rate and internal resistance that solve secondary cell are difficult to the technical problem improved simultaneously, first the present invention provides a kind of electrode for secondary battery, the electrode material comprising collector and coating or fill on a current collector, described electrode material comprises electrode active material, additive for electrode, conductive agent, binding agent, described additive for electrode is at least one in VIB, VIIB of agraphitic carbon load or group VIII metal, and the mass percentage that described additive for electrode accounts for electrode for secondary battery active material is no more than 10wt%.
In order to the low temperature discharge rate and internal resistance that solve secondary cell are difficult to the technical problem improved simultaneously, the present invention and then a kind of preparation method of electrode for secondary battery is provided, apply after electrode material being made into electrode slurry or fill on a current collector, then calendering, dry, section, described electrode material comprises electrode active material, additive for electrode, conductive agent, binding agent; Described additive for electrode is at least one in VIB, VIIB of agraphitic carbon load or group VIII metal, and the mass percentage that described additive for electrode accounts for electrode for secondary battery active material is no more than 10wt%, the preparation method of described additive for electrode is: mixed by the soluble salt solutions of amorphous carbon with at least one VIB, VIIB or group VIII metal, with reducing agent, the soluble-salt of described VIB, VIIB or group VIII metal is reduced to corresponding metal again, then washing, drying obtain.
In order to the low temperature discharge rate and internal resistance that solve secondary cell are difficult to the technical problem improved simultaneously, the present invention also provides a kind of secondary cell, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, and described positive pole and/or negative pole are electrode provided by the invention.
Use electrode for secondary battery provided by the invention, improve the low temperature discharge rate of secondary cell, reduce internal resistance of rechargeable battery: at nickel-hydrogen secondary cell-10 DEG C, the discharge rate of 3C electric discharge on average improves 3% simultaneously, at lithium rechargeable battery-10 DEG C, the discharge rate of 3C electric discharge on average improves 10.3%, and at NI-G secondary cell-10 DEG C, the discharge rate of 3C electric discharge on average improves 9.7%; Under normal temperature, nickel-hydrogen secondary cell internal resistance on average reduces by 0.02 milliohm, and internal resistance of lithium-ion secondary battery on average reduces by 0.1 milliohm, and NI-G internal resistance of rechargeable battery on average reduces by 0.12 milliohm.In addition, the normal temperature heavy-current discharge rate (normal temperature 3C discharge rate) of battery, high temperature place after the performance such as capability retention (placing capability retention after 3 days for 60 DEG C), normal temperature 20C discharge platform mean voltage and overshoot leakage time all have improvement in various degree.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
First the present invention provides a kind of electrode for secondary battery, the electrode material comprising collector and coating or fill on a current collector, described electrode material comprises electrode active material, additive for electrode, conductive agent, binding agent, described additive for electrode is at least one in VIB, VIIB of agraphitic carbon load or group VIII metal, and the mass percentage that described additive for electrode accounts for electrode for secondary battery active material is no more than 10wt%.In electrode material, add amorphous carbon can play and improve secondary cell low temperature charging-discharging performances.But because the conductivity of amorphous carbon is not good enough, cause the internal resistance of cell to increase.By the metal of some kind of load on amorphous carbon can improve be used alone amorphous carbon time the internal resistance of cell larger defect.Inventor finds, if do not use the technical scheme of at least one in activated carbon supported VIB, VIIB or group VIII metal, but respectively to adding amorphous carbon and above-mentioned metal in secondary battery electrode material, then almost improvement result is not had to the internal resistance of cell.
Due to the limited quality of the electrode material that can hold on collector, additive for electrode consumption can reduce electrode active material content on a current collector too much, has adverse effect to secondary cell performance.Therefore, according to the general consumption of additive in this area, the 10wt% of electrode for secondary battery active material quality is namely no more than.
According to the electrode for secondary battery that the specific embodiment of the invention provides, VIB, VIIB of agraphitic carbon load or the quality of group VIII metal preferably account for 2 ~ 5wt% of agraphitic carbon quality.Can better improve the low temperature discharge rate of battery simultaneously and reduce the internal resistance of cell like this, in addition, cost be also lower.
According to the electrode for secondary battery that the specific embodiment of the invention provides, at least one in VIB, VIIB or the preferred ruthenium of group VIII metal, nickel, manganese, cobalt, tungsten, molybdenum, the more preferably at least one of nickel, cobalt.These two kinds of metals than cheap other VIB, VIIB or group VIII metal, therefore preferably.
According to the electrode for secondary battery that the specific embodiment of the invention provides, the average grain diameter of agraphitic carbon preferably 0.1 ~ 15 μm.When the average grain diameter of amorphous carbon is within the scope of this, better to the tack of collector, coating (or filling) to collector after be not easy to come off, and also have good improvement to battery low temperature discharge rate.
According to the electrode for secondary battery that the specific embodiment of the invention provides, the specific area preferably 600 ~ 2500m of agraphitic carbon
2when the specific area of/g amorphous carbon is within the scope of this, comparatively strong to the adsorptivity of solid particle, carried metal ratio is easier to, and has good improvement to battery low temperature performance simultaneously.
According to the electrode for secondary battery that the specific embodiment of the invention provides, the porosity of agraphitic carbon is preferably not less than 40%.Be not less than 40% the improvement of porosity to battery low temperature discharge rate larger.
According to the electrode for secondary battery that the specific embodiment of the invention provides, additive for electrode bulk density is on a current collector 450 × 10
4~ 200 × 10
5g/m
3.Additive for electrode is when the surface density of collection liquid surface is within the scope of this, and the electrode material on collector is not easy material, better to the tack of collector base material, therefore preferably.
The present invention and then a kind of preparation method of electrode for secondary battery is provided, apply after electrode material being made into electrode slurry or fill on a current collector, then calendering, dry, section, described electrode material comprises electrode active material, additive for electrode, conductive agent, binding agent; Described additive for electrode is at least one in VIB, VIIB of agraphitic carbon load or group VIII metal, and the mass percentage that described additive for electrode accounts for electrode for secondary battery active material is no more than 10wt%, the preparation method of described additive for electrode is: mixed by the soluble salt solutions of amorphous carbon with at least one VIB, VIIB or group VIII metal, with reducing agent, the soluble-salt of described VIB, VIIB or group VIII metal is reduced to corresponding metal again, then washing, drying obtain.
The example of the soluble-salt of VIB, VIIB or group VIII metal as the nitrate of above-mentioned metal, such as nickel nitrate, cobalt nitrate, manganese nitrate etc.The example of reducing agent has: potassium borohydride, sodium borohydride.The temperature of reduction reaction is not particularly limited, and can be metal by metal salt back, generally at 50 ~ 70 DEG C.
So-called amorphous carbon, does not refer to the shape that these materials exist, and refers to its internal structure.In fact their internal structure is not real amorphous body, but there is the crystal with graphite one spline structure, the layer structure just formed by carbon atom hexagon ring plain is messy and irregular, Crystallization defectiveness, and crystal grain is small, containing a small amount of impurity.The object lesson of amorphous carbon has: charcoal, coke, active carbon, carbon black, carbon fiber, glassy carbon, CNT (carbon nano-tube).
The specific embodiment of the invention also provides a kind of secondary cell, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, the electrode that described positive pole and/or negative pole provide for the specific embodiment of the invention.The manufacture method of the electrode for secondary battery that the specific embodiment of the invention provides and secondary cell is that those skilled in the art are known, does not repeat them here.
Embodiment 1
1. the preparation of additive for electrode:
Take 10g active carbon (average grain diameter 5 μm, specific area 2300m
2/ g, porosity 40%) in 1000ml beaker, add 100ml water and stir, then add the nickel nitrate 100ml that concentration is 1mol/L wherein, slowly instillation 2mol/L potassium borohydride 100ml, stirring reaction 40min at 60 DEG C.Wash active carbon with water 5 times after reaction terminates, 100 DEG C of vacuumize 1 hour, more dried product is immersed concentration is stir 40min in the sodium hydroxide solution of 100ml 2mol/L, then spends deionized water, filter, 100 DEG C of vacuumize 1 hour.Weigh the weight difference before and after activated carbon supported metal nickel, calculating nickel load capacity is on the activated carbon 3.3wt%.
2. Ni-MH secondary battery anode sheet preparation:
What the additive for electrode that the step 1 of 2 weight portions obtains is added 100 weight portions covers in cobalt ball nickel, add 1 weight portion conductive agent cobalt protoxide, binding agent is made with the CMC of 4 weight portions and the PTFE of 5 weight portions, add suitable quantity of water mixing, stir, be evenly coated in nickel foam, 100 DEG C of dryings, calendering, section, obtain the positive plate of length × wide × thick=240mm × 33.5mm × 0.38mm.Anode additive and cover the dressing amount of cobalt ball nickel respectively on every sheet positive plate: 0.14g, 7g.Anode additive accounts for the 2wt% of the quality covering cobalt ball nickel, and the bulk density of anode additive on plus plate current-collecting body is 4.58 × 10
4g/m
3.
3. nickel-hydrogen secondary battery negative electrode sheet preparation:
The additive for electrode that 3 weight portion steps 1 obtain is added the AB of 100 weight portions
5type hydrogen storage alloy (La
0.3ce
0.5ni
3.5co
1al
amn
b, a+b=0.5) in, add 1 weight portion conductive agent nickel powder, make binding agent with the CMC of 4 weight portions and the PTFE of 5 weight portions, add suitable quantity of water mixing, stir, be evenly coated on nickel plated steel strip, drying, compressing tablet, obtains the negative plate of long × wide × thick=295mm × 34.64mm × 0.24mm.On every sheet negative plate, the dressing amount of cathode additive agent and storage light-alloy respectively: 0.42g, 14g.Cathode additive agent accounts for the 3wt% of the quality covering cobalt ball nickel, and the bulk density of cathode additive agent on negative current collector is 1.71 × 10
5g/m
3.
4. nickel-hydrogen secondary cell preparation:
By positive and negative plate therebetween one deck polypropylene diaphragm (Japanese Coudé is precious, 27R type) winding obtained above, inject the KOH solution 5ml of 6mol/L, block, sealing, then under normal temperature, 0.1C charges 3 hours, obtains finished product SC model Ni-MH battery.
Embodiment 2
Change nickel nitrate into cobalt nitrate, active carbon changes carbon fiber into, and anode additive accounts for the 2.5wt% of the quality covering cobalt ball nickel, and the bulk density of anode additive on plus plate current-collecting body is 4.62 × 10
4g/m
3, the bulk density of cathode additive agent on negative current collector is 1.68 × 10
5g/m
3, other are with embodiment 1.
Embodiment 3
Nickel nitrate is changed into nickel nitrate, cobalt nitrate salt-mixture (mol ratio is 1: 1), active carbon changes vitreous carbon into, and cathode additive agent accounts for the 4wt% of the quality covering cobalt ball nickel, and the bulk density of anode additive on plus plate current-collecting body is 4.80 × 10
4g/m
3, the bulk density of cathode additive agent on negative current collector is 1.76 × 10
5g/m
3, other are with embodiment 1.
Embodiment 4
1. the preparation of additive for electrode:
Take 10g active carbon (average grain diameter 3 μm, specific area 2000m
2/ g, porosity 40%) in 1000ml beaker, add 100ml water and stir, then add the nickel nitrate 100ml that concentration is 1mol/L wherein, slowly instillation 2mol/L potassium borohydride 100ml, stirring reaction 40min at 60 DEG C.Wash active carbon with water 5 times after reaction terminates, 100 DEG C of vacuumize 1 hour, more dried product is immersed concentration is stir 40min in the sodium hydroxide lye of 100ml 2mol/L, then spends deionized water, filter, 100 DEG C of vacuumize 1 hour.Weigh the weight difference before and after activated carbon supported metal nickel, calculating nickel load capacity is on the activated carbon 2.8wt%.
2. lithium-ion secondary battery positive plate preparation:
The additive for electrode that the step 1 of 2 weight portions obtains is added in the cobalt acid lithium of 100 weight portions, add 1 weight portion conductive agent acetylene black, binding agent is made with the PVDF of 5 weight portions, add 40 weight portion NMP to mix, stir, be evenly coated on aluminium foil, 80 DEG C of dryings, calendering, section, obtain the positive plate of length × wide × thick=240mm × 33.5mm × 0.38mm.On every sheet positive plate, the dressing amount of anode additive and cobalt acid lithium respectively: 0.14g, 7g.Anode additive accounts for the 2wt% of the quality of cobalt acid lithium, and the bulk density of anode additive on plus plate current-collecting body is 4.58 × 10
4g/m
3.
3. lithium ion secondary battery negative pole sheet preparation:
The additive for electrode that 3 weight portion steps 1 obtain is added in the graphite of 100 weight portions, makees binding agent with 5 weight portion PVDF, add 40 weight portion NMP and mix, stir, be evenly coated on Copper Foil, 80 DEG C of dryings, compressing tablet, obtains the negative plate of long × wide × thick=295mm × 34.64mm × 0.24mm.On every sheet negative plate, the dressing amount of cathode additive agent and graphite respectively: 0.42g, 14g.Cathode additive agent accounts for the 3wt% of the quality of graphite, and the bulk density of cathode additive agent on negative current collector is 1.71 × 10
5g/m
3.
4. lithium rechargeable battery preparation:
By positive and negative plate therebetween one deck Celgard2400 membrane winding obtained above, inject 1mol/L LiPF
6solution (solvent is mol ratio EC: DEC=1: 1) 2ml, block, sealing, 4.1V charges 30 minutes, obtains finished product SC type lithium ion battery.
Embodiment 5
Change nickel nitrate into cobalt nitrate, active carbon changes carbon fiber into, and anode additive accounts for the 3wt% of the quality of cobalt acid lithium, and the bulk density of anode additive on plus plate current-collecting body is 4.55 × 10
4g/m
3, the bulk density of cathode additive agent on negative current collector is 1.79 × 10
5g/m
3, other are with embodiment 4.
Embodiment 6
Nickel nitrate in embodiment is changed into nickel nitrate, cobalt nitrate salt-mixture (mol ratio is 1: 1), anode additive accounts for the 2.5wt% of the quality of cobalt acid lithium, cathode additive agent accounts for the 3.5wt% of the quality of graphite, and the bulk density of anode additive on plus plate current-collecting body is 4.67 × 10
4g/m
3, the bulk density of cathode additive agent on negative current collector is 1.71 × 10
5g/m
3, other are with embodiment 4.
Embodiment 7
1. the preparation of additive for electrode:
Take 10g active carbon (average grain diameter 5 μm, specific area 1800m
2/ g, porosity 43%) in 1000ml beaker, add 100ml water and stir, then add the nickel nitrate 100ml that concentration is 1mo1/L wherein, slowly instillation 2mol/L potassium borohydride 100ml, stirring reaction 40min at 60 DEG C.Wash active carbon with water 5 times after reaction terminates, 100 DEG C of vacuumize 1 hour, more dried product is immersed concentration is stir 40min in the sodium hydroxide lye of 100ml 2mol/L, then spends deionized water, filter, 100 DEG C of vacuumize 1 hour.Weigh the weight difference before and after activated carbon supported metal nickel, calculating nickel load capacity is on the activated carbon 4.2wt%.
2. NI-G secondary battery positive plate preparation:
What the additive for electrode that 2 weight portion steps 1 obtain is added 100 weight portions covers in cobalt ball nickel, add 1 weight portion conductive agent cobalt protoxide, binding agent is made with the CMC of 4 weight portions and the PTFE of 5 weight portions, add suitable quantity of water mixing, stir, be evenly coated in nickel foam, 100 DEG C of dryings, calendering, section, obtain the positive plate of length × wide × thick=240mm × 33.5mm × 0.38mm.Anode additive and cover the dressing amount of cobalt ball nickel respectively on every sheet positive plate: 0.14g, 14g.Anode additive accounts for the 2wt% covering cobalt ball nickel, and anode additive (amorphous carbon nickel-loaded) bulk density on plus plate current-collecting body is 4.58 × 10
4g/m
3.
3. NI-G secondary battery anode piece preparation:
The additive for electrode that 3 weight portion steps 1 obtain is added in the cadmium oxide of 100 weight portions, add 1 weight portion conductive agent nickel powder, binding agent is made with the CMC of 4 weight portions and the PTFE of 5 weight portions, add suitable quantity of water mixing, stir, be evenly coated on nickel plated steel strip, 100 DEG C of dryings, compressing tablet, obtains the negative plate of long × wide × thick=295mm × 34.64mm × 0.27mm.On every sheet negative plate, the dressing amount of cathode additive agent and cadmium oxide respectively: 0.42g, 14g.Cathode additive agent accounts for the 3wt% of cadmium oxide, and cathode additive agent (amorphous carbon nickel-loaded) bulk density on negative current collector is 1.71 × 10
5g/m
3.
4. NI-G secondary cell preparation:
By positive and negative plate therebetween one deck polypropylene diaphragm (Japanese Coudé is precious, 27R type) winding obtained above, inject the KOH solution 5ml of 6mol/L, block, sealing, 0.1C charges 14 hours, obtains finished product SC model nickel-cadmium cell.
Embodiment 8
Change nickel nitrate in embodiment into cobalt nitrate, anode additive accounts for the 2.8wt% covering cobalt ball nickel, and cathode additive agent accounts for the 4wt% of cadmium oxide, and other are with embodiment 7.
Embodiment 9
Nickel nitrate in embodiment is changed into nickel nitrate, cobalt nitrate salt-mixture (mol ratio is 1: 1), the bulk density of anode additive on plus plate current-collecting body is 4.82 × 10
4g/m
3, the bulk density of cathode additive agent on negative current collector is 1.81 × 10
5g/m
3, other are with embodiment 7.
Comparative example 1
The additive of positive and negative electrode changes the active carbon of same weight unmodified into, and other are completely with embodiment 1.
Comparative example 2
The additive of positive and negative electrode changes the active carbon of same weight unmodified into, and other are completely with embodiment 4.
Comparative example 3
The additive of positive and negative electrode changes the active carbon of same weight unmodified into, and other are completely with embodiment 7.
Comparative example 4
Positive and negative electrode does not add additive for electrode, and other are completely with embodiment 1.
Comparative example 5
Positive and negative electrode does not add additive for electrode, and other are completely with embodiment 4.
Comparative example 6
Positive and negative electrode does not add additive for electrode, and other are completely with embodiment 7
Battery performance test:
By test battery internal resistance by the following method respectively after the Battery formation partial volume of embodiment and comparative example:
1. heavy-current discharge performance (normal temperature 3C discharge rate) and discharge platform mean voltage: 1C charges 75 minutes at normal temperatures, and then 3C is discharged to 0.8V, measuring current discharge capacity and mean voltage.Discharge platform mean voltage refers to the magnitude of voltage that intermediate value discharge time of tester record in discharge test process is corresponding.Intermediate value discharge time is the half of releasing whole electricity required time.Mean voltage higher explanation heavy-current discharge effect is better.
2. high temperature places capability retention (placing capability retention after 3 days for 60 DEG C): placed 3 days at 60 DEG C by battery, test battery residual capacity, residual capacity obtains capability retention than battery actual capacity.
3. low-temperature high-current discharge performance (-10 DEG C of 5C discharge rates): at battery being placed in-10 DEG C 4 hours, then 5C is discharged to 0.6V, test for low temperature discharge rate.
4. overcharge leakage performance (2C overcharges the leakage time): battery 2C is overcharged (namely continue after battery is full of electricity charging), observe when leakage, and record the leakage time.
The BK7024 type battery charging and discharging perseverance test that above-mentioned performance all uses Guangzhou Lanqi Electronic Industrial Co., Ltd. to produce.
Table 1 battery performance test result
Embodiment 1 ~ 3, comparative example 1 and 4 is Ni-MH battery; Embodiment 4 ~ 6, comparative example 2 and 5 is lithium ion battery; Embodiment 7 ~ 9, comparative example 3 and 6 is nickel-cadmium cell.
The operating process of the test result that comprehensive analysis is shown and each embodiment and comparative example is known:
1. the specific embodiment of the invention provide Ni-MH battery, nickel-cadmium cell, the normal temperature 3C discharge rate of lithium ion battery ,-10 DEG C of 3C discharge rates, discharge platform mean voltage, the internal resistance of cell, 60 DEG C place 3 days capability retentions and overcharge the performances such as leakage time all compared with on electrode only containing the improvement had during amorphous carbon in various degree.Wherein, the improvement overcharging leakage time and 60 DEG C of placements, 3 days these two performances of capability retention are that inventor never expects, so tool of the present invention has an unexpected effect.
2. the amorphous carbon of load metal of the present invention makes the internal resistance of cell have as the amorphous carbon of additive for electrode metal of the present invention Bi not load as additive to a certain degree to reduce.Do not use the secondary cell (embodiment 4,5,6) of any additive for electrode although internal resistance is little, but the low temperature discharge rate of battery (-10 DEG C of 3C discharge rates), normal temperature heavy-current discharge rate (normal temperature 3C discharge rate), overcharging leakage time and 60 DEG C, to place the corresponding secondary cell that the performances such as 3 days capability retentions all provide compared with the specific embodiment of the invention low, that is, the combination property of secondary cell that provides of prior art is not as the secondary cell of the specific embodiment of the invention.So generally speaking, the present invention has outstanding substantial effect and significant progress.
Table 2 embodiment of the present invention chemical reagent used and raw material
| Chemical reagent/raw material | Purity | Source |
| Nickel nitrate | ≥99.8％ | Guangzhou Chemical Reagent Factory |
| Cobalt nitrate | ≥99.8％ | Guangzhou Chemical Reagent Factory |
| Active carbon | ≥99.8％ | Guangzhou Chemical Reagent Factory |
| Nickel hydroxide | ≥99.8％ | Cologne, Henan Electrical Appliances Co., Ltd |
| AB 5Hydrogen bearing alloy | ≥99.8％ | Xiamen tungsten industry |
| Cobalt acid lithium | ≥99.8％ | Changsha is auspicious auspicious |
| Delanium | ≥99.8％ | Shenzhen Bei Terui |
| Cadmium oxide | ≥99.8％ | Shenzhen Ya Lande |
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. at a kind of electrode for secondary battery, the electrode material comprising collector and coating or fill on a current collector, described electrode material comprises electrode active material, additive for electrode, conductive agent, binding agent, it is characterized in that, described additive for electrode is at least one in the ruthenium of agraphitic carbon load, nickel, manganese, cobalt, tungsten, molybdenum; The mass percentage that the metal of described agraphitic carbon load accounts for agraphitic carbon is 2 ~ 5wt%; The porosity of described agraphitic carbon is not less than 40%; The mass percentage that described additive for electrode accounts for electrode for secondary battery active material is no more than 10wt%; The metal of described agraphitic carbon load is mixed by the soluble salt solutions of agraphitic carbon with at least one ruthenium, nickel, manganese, cobalt, tungsten, molybdenum, then with reducing agent, the soluble salt of described ruthenium, nickel, manganese, cobalt, tungsten, molybdenum is reduced to corresponding metal gained.
2. electrode for secondary battery as claimed in claim 1, it is characterized in that, described metal is selected from least one in nickel, cobalt.
3. electrode for secondary battery as claimed in claim 1, is characterized in that, the average grain diameter of described agraphitic carbon 0.1 ~ 15 μm.
4. electrode for secondary battery as claimed in claim 1, is characterized in that, the specific area 600 ~ 2500m of described agraphitic carbon
2/ g.
5. a preparation method for electrode for secondary battery, applies after electrode material being made into electrode slurry or fills on a current collector, then calendering, dry, section, and described electrode material comprises electrode active material, additive for electrode, conductive agent, binding agent; It is characterized in that, described additive for electrode is at least one in the ruthenium of agraphitic carbon load, nickel, manganese, cobalt, tungsten, molybdenum, and the mass percentage that described additive for electrode accounts for electrode for secondary battery active material is no more than 10wt%, the preparation method of described additive for electrode is: mixed by the soluble salt solutions of amorphous carbon with at least one ruthenium, nickel, manganese, cobalt, tungsten, molybdenum, with reducing agent, the soluble-salt of described ruthenium, nickel, manganese, cobalt, tungsten, molybdenum is reduced to corresponding metal again, then washing, drying obtain; The mass percentage that the metal of described agraphitic carbon load accounts for agraphitic carbon is 2 ~ 5wt%, and the porosity of described agraphitic carbon is not less than 40%.
6. the preparation method of electrode for secondary battery as claimed in claim 5, it is characterized in that, described metal is selected from least one in nickel, cobalt.
7. the preparation method of electrode for secondary battery as claimed in claim 5, is characterized in that, the average grain diameter of described agraphitic carbon 0.1 ~ 15 μm.
8. the preparation method of electrode for secondary battery as claimed in claim 5, is characterized in that, the specific area 600 ~ 2500m of described agraphitic carbon
2/ g.
9. a secondary cell, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, and electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, it is characterized in that, described positive pole and/or negative pole are the electrode described in claim 1 ~ 4 any one.
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| CN1462081A (en) * | 2002-05-28 | 2003-12-17 | 沈阳金纳新材料有限公司 | High performance rechargeable battery |
| CN1442925A (en) * | 2002-10-24 | 2003-09-17 | 深圳市镍霸实业有限公司 | Technology for improving storage performance of nickel-hydrogen rechargeable battery |
| CN1728423A (en) * | 2004-07-30 | 2006-02-01 | 松下电器产业株式会社 | Negative electrode and nickel metal hydride storage battery using the same |
| CN101549865A (en) * | 2009-05-12 | 2009-10-07 | 复旦大学 | Method for modifying carbon nano-tube by nickel nanometer particles |
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| CN102208596A (en) | 2011-10-05 |
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