CN102544502B - Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery - Google Patents
Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery Download PDFInfo
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Abstract
The invention discloses an anode and cathode conductive additive for a secondary lithium battery, a method for preparing the conductive additive, and a method for preparing the secondary lithium battery. The conductive additive is graphene or a mixture of the graphene and other conductive materials, is graphene powder or mixture powder of graphene and other conductive materials, and also can be graphene or mixture conductive agent slurry of the graphene and other conductive materials, which is uniformly dispersed in water or an organic solvent or in water or an organic solvent which contains a dispersing agent. The graphene conductive additive is suitable for preparing the anode and cathode of the secondary lithium battery, and has the obvious advantage of improving the high-rate performance and cycle stability of the secondary lithium battery compared with other conductive additives at present.
Description
Technical field
The invention belongs to energy storage material field, be specifically related to a kind of conductive additive for lithium secondary battery and preparation method thereof and relevant cell art.
Background technology
Since the beginning of the nineties in last century, first commercialization lithium secondary battery product came out, lithium secondary battery just obtains a wide range of applications in portable type electronic product because of its high power capacity, high voltage platform, long-life and high security.The problem concerning survival and development of mankind along with fossil energy is exhausted and global warming etc. becomes increasingly conspicuous, and people constantly expand for the demand of clean energy resource, and consequent New Energy Industry has very huge development prospect and market scale.People generally expect that lithium secondary battery will fully develop talents in the industry, especially large-scale energy storage device and with electric automobile be representative electrokinetic cell in application prospect attracted global sight especially.For this reason, the research and development that a large amount of manpower and materials carry out novel high-performance lithium secondary battery have all been dropped in countries in the world, to meet the higher requirement that large-sized power battery and energy-storage battery propose in energy density, power density, cycle life and fail safe etc.
As the one of battery, lithium secondary battery requires that its electrode has good conductivity naturally.The conductivity of the positive electrode active materials such as LiFePO4, LiMn2O4, ternary material conventional at present itself is not all very high, there is larger contact resistance between positive electrode particle simultaneously.Therefore, all need to add in positive pole preparation there is high conductivity additive to improve the electron transfer rate in positive pole.Graphite-like active material conventional in negative pole, although itself have good conductivity, but in order to overcome intergranular contact resistance, when especially will realize large multiplying power discharging, still need to improve its conductivity by adding conductive agent, its electron conduction ability and lithium ion ability of deintercalation from graphite are reached to balance.Therefore, conductive additive plays an important role in the lithium secondary battery, is also the part that of this industry is indispensable.
At present, commercial conductive agent, based on material with carbon element, mainly comprises the electrically conductive graphite of low side, acetylene black, Super P-Li etc., and high-end carbon nanotube conducting additive.Although the former low price, be difficult to meet the lasting discharge and recharge of battery under high magnification; Although the latter's performance is outstanding, be particularly useful for high-power battery, its practical application in the lithium secondary battery of the price limit of its costliness.Therefore, the high-performance conductive additive of development of new cheapness is very urgent.
Graphene is the class new carbon found in 2004, and it has unique two-dimensional nanostructure and novel physicochemical properties, and therefore receive the extensive concern of scientific circles and industrial circle, application prospect is very wide.Graphene has high conductivity, and this lays a good foundation for it becomes a successful conductive additive.Secondly, the two-dimensional nanostructure of Graphene had both been different from the three-dimensional conductive particle such as electrically conductive graphite or Super P-Li, was also different from the carbon nano-tube of one dimension.As film, the Graphene of " pliable and tough " is easy to be wrapped in around electrode active material particles, and forming surface contacts, and is easy to form three-dimensional conductive network.On the other hand, the heat conductivility that Graphene is good also benefits for the lifting of battery high-temperature behavior and cyclical stability.In the national inventing patent (application number 201010514810.0) applied in our prior, by the method improved, can realize the extensive preparation of high-quality graphene, and (significantly lower than carbon nano-tube) with low cost.Therefore, graphene conductive additive has obvious advantage compared to other conductive agent products.
Summary of the invention
Primary technical problem to be solved by this invention provides a kind of positive pole negative conductive additive for lithium secondary battery for the above-mentioned state of the art, it realizes electronics fast transferring in the electrodes, be beneficial to high power charging-discharging, high-temperature behavior and the cycle life of battery can be promoted simultaneously.
Another technical problem to be solved by this invention is the preparation method providing a kind of positive pole negative conductive additive for lithium secondary battery for the above-mentioned state of the art, and its method is simple, easily implements.
Another technical problem to be solved by this invention is the preparation method providing a kind of relevant lithium secondary battery for the above-mentioned state of the art.
The technical scheme that the present invention adopts for the above-mentioned primary technical problem of solution is: a kind of positive pole negative conductive additive for lithium secondary battery, it is characterized in that adopting graphene conductive additive, for the mixture of pure Graphene or Graphene and other electric conducting material, in described Graphene and the mixture of other electric conducting material, the mass percent shared by Graphene is between 1%-99%.
As improvement, described graphene conductive additive is powder, or for being scattered in the graphene conductive additive slurry in water or organic solvent, or for being scattered in the graphene conductive additive slurry in water containing dispersant or organic solvent, in described graphene conductive additive slurry, the mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30%, and the mass percentage of described dispersant in graphene conductive additive slurry is 0.1%-10%.
Preferably, described Graphene is monoatomic layer graphite, or the graphene nanometer sheet of the atom number of plies between 2-15 layer, and its lamella lateral dimension is between 0.1-100 μm.
Preferably, other described electric conducting material is at least the one in electrically conductive graphite, conductive carbon black, acetylene black, Super P-Li, carbon nano-tube (CNTs), carbon nano-fiber, gas-phase growth of carbon fibre (VGCF), conductive silver particle, conductive copper particle, conductive aluminum particle, conductive silver fiber, conductive copper fiber, conductive aluminum fiber, or several combinations.
Preferably, described organic solvent is 1-METHYLPYRROLIDONE, ethanol, acetone, pyridine, aniline, pentamethylene, cyclohexane, normal-butyl ring penta cycloalkanes, 2, the combination of one or more in 2-dimethylhexane, 2,3-dimethylhexanes, 2,4-dimethyl pentanes, five methylheptane.
Preferably, described dispersant is at least the one in polyvinylpyrrolidone, polyvinyl alcohol, Pluoronic F127, PluoronicP123, Pluronic F68, polyoxyethylene laurel ether, or several combinations.
The technical scheme that the present invention adopts for solution another technical problem above-mentioned is: a kind of preparation method of the positive pole negative conductive additive for lithium secondary battery, it is characterized in that the method is selected to carry out from step by following:
1) graphene conductive additive agent powder is prepared by the one of the following two kinds method:
A) graphene powder and other electric conducting material powder are obtained compound powder by mechanical mixture, make described Graphene and the mixture of other electric conducting material, the mass percent shared by its Graphene is between 1%-99%;
Or,
B) be by Graphene, or the mixture of Graphene and other electric conducting material adds water or organic solvent, or by Graphene, or the mixture of Graphene and other electric conducting material adds in water containing dispersant or organic solvent, by ultrasonic process or mechanical mixture, or above-mentioned ultrasonic process or mechanical mixture are combined to form homodisperse colloid, again by centrifugal, a kind of method in suction filtration or press filtration obtains the conductive additive slurry concentrated, further drying removing residual water or solvent and dispersant, obtain graphene conductive additive agent powder material, make described Graphene and the mixture of other electric conducting material, mass percent shared by its Graphene is between 1%-99%,
2) the conductive additive slurry be scattered in water or organic solvent is prepared by the following method:
By Graphene, or the mixture of Graphene and other electric conducting material adds in water or organic solvent, in described Graphene and the mixture of other electric conducting material, mass percent shared by Graphene is between 1%-99%, by ultrasonic process or mechanical mixture, or above-mentioned ultrasonic process or mechanical mixing be combined to form homodisperse colloid, again by centrifugal, conductive additive slurry is obtained after a kind of method in suction filtration or press filtration is concentrated, in described graphene conductive additive slurry, the mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30%,
3) the graphene conductive additive slurry be scattered in water containing dispersant or organic solvent is prepared by the following method:
First dispersant is dissolved in water or organic solvent, add Graphene subsequently, or the mixture of Graphene and other electric conducting material, in described Graphene and the mixture of other electric conducting material, mass percent shared by Graphene is between 1%-99%, by ultrasonic process or mechanical mixture, or this above-mentioned ultrasonic process or mechanical mixture be combined to form homodisperse colloid, again by centrifugal, conductive additive slurry is obtained after a kind of method in suction filtration or press filtration is concentrated, in described graphene conductive additive slurry, the mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30%, the mass percentage of described dispersant in graphene conductive additive slurry is 0.1%-10%.
Preferably, mechanical mixture adopts the one in ball milling, sand milling or dry stirring for powder.
Preferably, mechanical mixture adopts the one in high-energy stirring, high speed shear or sand milling for liquid phase.
Preferably, ultrasonic process adopts probe type ultrasonic equipment or ultrasonic cleaning machine, power 100-3000W, ultrasonic time 5-60 minute.
Preferably, the dry one adopted in constant pressure and dry, vacuumize, spraying dry or freeze drying.
The technical scheme that the present invention adopts for solution another technical problem above-mentioned is: a kind of lithium secondary battery preparation method using positive pole negative conductive additive, it is characterized in that carrying out according to the following steps:
Graphene conductive additive agent powder or slurry and binding agent are scattered in water or organic solvent by a certain percentage, after stirring, add cathode plate for lithium secondary battery or negative active core-shell material, high-speed stirred is dispersed in uniform sizing material, the conventional method prepared according to lithium secondary battery electrode subsequently prepares negative or positive electrode sheet, and is assembled into lithium secondary battery;
When described graphene conductive additive adopts powder, be the mixture of pure Graphene or Graphene and other electric conducting material, in described Graphene and the mixture of other electric conducting material, the mass percent shared by Graphene is between 1%-99%; When adopting slurry, for being scattered in the graphene conductive additive slurry in water or organic solvent, or for being scattered in the graphene conductive additive slurry in water containing dispersant or organic solvent, in described graphene conductive additive slurry, the mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30%, and the mass percentage of described dispersant in graphene conductive additive slurry is 0.1%-10%;
Described binding agent is Kynoar, or the one in polytetrafluoroethylene, in polyvinyl alcohol, sodium carboxymethylcellulose, methylcellulose, hydroxypropyl methylcellulose, carboxymethyl hydroxyethyl cellulose or hydroxypropyl cellulose, the mass percent of binding agent in cathode plate for lithium secondary battery or negative pole is 1%-10%.
Described organic solvent be 1-METHYLPYRROLIDONE, ethanol or, acetone, pyridine, aniline, pentamethylene, cyclohexane, normal-butyl ring penta cycloalkanes, 2,2-dimethylhexane, 2, the combination of one or more in 3-dimethylhexane, 2,4-dimethyl pentanes, five methylheptane.
The quality of Graphene contained in graphene conductive additive agent powder or slurry or the mass ratio of the gross mass of Graphene and other electric conducting material mixture and binding agent are 0.1 ~ 10: 1.
Graphene quality contained in graphene conductive additive agent powder or slurry or the gross mass of Graphene and other electric conducting material mixture, adding the quality sum of binding agent, is 1: 3 ~ 50 with the mass ratio of organic solvent.
Preferably, lithium secondary battery positive active material comprises LiFePO4, lithium ferric manganese phosphate, cobalt acid lithium, spinel lithium manganate, layered lithium manganate, stratiform lithium nickel cobalt dioxide, spinel nickel LiMn2O4, the rich lithium nickel ion doped of stratiform, stratiform cobalt nickel lithium manganate ternary material or lithium vanadate; Lithium secondary battery anode active material comprises flaky graphite, modified natural graphite microballoon, artificial graphite microspheres, carbonaceous mesophase spherules, lithium titanate, nano-silicon or Si-C composite material.
Preferably, the addition of graphene conductive additive in cathode plate for lithium secondary battery is 0.5%-30%, mass percentage, calculates according to the solid masses of the mixture of Graphene or Graphene and other electric conducting material; The addition of graphene conductive additive in lithium secondary battery anode is 0.5%-10%, mass percentage, calculates according to the solid masses of Graphene or Graphene and acetylene black mixture.
Compared with prior art, the invention has the advantages that: compared with current commercial electrically conductive graphite, conductive carbon black, SuperP-Li and carbon nanotube conducting additive, Graphene not only has high conductivity, and the two-dimensional nanostructure of its uniqueness can form the three-dimensional conductive network be wrapped in around both positive and negative polarity active material very effectively, two dimension is laminar structured simultaneously can with the mode of face contact and electrode active material close contact, thus realize electronics fast transferring in the electrodes, be beneficial to high power charging-discharging.Meanwhile, the thermal conductivity that Graphene is good has positive meaning for conducting the heat produced in charge and discharge process fast, can promote high-temperature behavior and the cycle life of battery.In addition, the specific area that Graphene is huge is also conducive to the raising of battery performance for the good absorption of electrolyte and maintenance effect.Also it is pointed out that, compared with high-end carbon nano-tube, the preparation cost of Graphene is lower, therefore has more advantage in actual applications.By the charge-discharge performance test result display carried out after using graphene conductive agent multiple different lithium anode of secondary battery, negative pole system, graphene conductive additive is obvious for the castering action of battery high rate performance, and be better than current commercial conductive additive, be a superior performance, and there is the novel conductive additive product of great market prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of the lithium iron phosphate positive material adding graphene conductive agent.
The discharge curve of (right side) battery when Fig. 2 a, 2b are graphene conductive additive (left side) and the Super P-Li conductive additive adding same mass percentage (15%) in identical lithium iron phosphate positive material respectively.Result shows, and graphene conductive additive is obviously better than commercial Super P-Li conductive additive to the lifting of battery high rate performance.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 5 grams of 1-METHYLPYRROLIDONEs, then add 0.6g graphene powder conductive additive, stir.Add 3.2g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 142mAh/g, 10C, discharge capacity is 110mAh/g, 30C, discharge capacity is 80mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 2
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 5 grams of 1-METHYLPYRROLIDONEs, then add 0.2g graphene powder conductive additive, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 140mAh/g, 10C, discharge capacity is 100mAh/g, 30C, discharge capacity is 60mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 3
Taking 1g Graphene solid adds in 100gN-methyl pyrrolidone, and ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 140mAh/g, 10C, discharge capacity is 105mAh/g, 30C, discharge capacity is 69mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 4
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 141mAh/g, 10C, discharge capacity is 103mAh/g, 30C, discharge capacity is 66mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 5
Take 0.2g Pluoronic P123, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 141mAh/g, 10C, discharge capacity is 104mAh/g, 30C, discharge capacity is 65mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 6
Take 0.2g polyvinyl alcohol, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 142mAh/g, 10C, discharge capacity is 102mAh/g, 30C, discharge capacity is 66mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 7
Take 0.2g polyoxyethylene laurel ether, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 141mAh/g, 10C, discharge capacity is 103mAh/g, 30C, discharge capacity is 66mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 8
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid and 2g Super P-Li powder subsequently, ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 10% (mass percent).
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then to add in 4g previous step obtained mass concentration be the electrocondution slurry of 10%, stir.Add 3.4g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 141mAh/g, 10C, discharge capacity is 108mAh/g, 30C, discharge capacity is 76mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 9
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid and 2g acetylene black powder subsequently, ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 10% (mass percent).
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then to add in 4g previous step obtained mass concentration be the electrocondution slurry of 10%, stir.Add 3.4g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 140mAh/g, 10C, discharge capacity is 109mAh/g, 30C, discharge capacity is 78mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 10
Take 0.4g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 2g Graphene solid and 1g carbon nano-tube subsequently, ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then to add in 4g previous step obtained mass concentration be the electrocondution slurry of 5%, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 143mAh/g, 10C, discharge capacity is 112mAh/g, 30C, discharge capacity is 81mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 11
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid, 1g acetylene black and 1g carbon nano-tube subsequently, ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then to add in 4g previous step obtained mass concentration be the electrocondution slurry of 5%, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 141mAh/g, 10C, discharge capacity is 107mAh/g, 30C, discharge capacity is 73mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 12
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid and 1.5g acetylene black and 0.5g conductive silver particle subsequently, ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then to add in 4g previous step obtained mass concentration be the electrocondution slurry of 5%, stir.Add 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 140mAh/g, 10C, discharge capacity is 111mAh/g, 30C, discharge capacity is 77mAh/g.Battery is under 1C after charge and discharge cycles 500 times, and capacity attenuation is less than 5%.
Embodiment 13
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g lithium cobaltate cathode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When recording 0.1C, discharge capacity is 145mAh/g, 1C, discharge capacity is 138mAh/g.
Embodiment 14
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g spinel lithium manganese oxide anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When recording 0.1C, discharge capacity is 132mAh/g, 1C, discharge capacity is 111mAh/g.
Embodiment 15
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g lithium nickel cobalt dioxide positive electrode active materials subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When recording 0.1C, discharge capacity is 175mAh/g, 1C, discharge capacity is 155mAh/g.
Embodiment 16
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then add the Graphene slurry that mass concentration obtained in 4g previous step is 5%, stir.Add 3.6g nickle cobalt lithium manganate ternary positive electrode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When recording 0.1C, discharge capacity is 188mAh/g, 1C, discharge capacity is 169mAh/g.
Embodiment 17
Taking 1g Graphene solid adds in 100gN-methyl pyrrolidone, and ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 3 grams of 1-METHYLPYRROLIDONEs, then add the Graphene slurry that mass concentration obtained in 2g previous step is 5%, stir.Add 3.7g modified natural graphite microballoon negative active core-shell material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on Copper Foil, dries under 100 DEG C of vacuum, after roll-in, make negative plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When recording 0.1C, capacity is 355mAh/g, 1C, capacity is 315mAh/g.
Embodiment 18
Take 1g polyvinylpyrrolidone, be dissolved in 100g water, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 3 grams of water, then add the Graphene slurry that mass concentration obtained in 2g previous step is 5%, stir.Add 3.7g modified natural graphite microballoon negative active core-shell material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on Copper Foil, dries under 100 DEG C of vacuum, after roll-in, make negative plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When recording 0.1C, capacity is 353mAh/g, 1C, capacity is 311mAh/g.
Embodiment 19
Taking 1g Graphene solid adds in 100gN-methyl pyrrolidone, and ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 3 grams of 1-METHYLPYRROLIDONEs, then add the Graphene slurry that mass concentration obtained in 2g previous step is 5%, stir.Add 3.7g carbonaceous mesophase spherules negative active core-shell material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on Copper Foil, dries under 100 DEG C of vacuum, after roll-in, make negative plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When recording 0.1C, capacity is 359mAh/g, 1C, capacity is 317mAh/g.
Embodiment 20
Taking 1g Graphene solid adds in 100gN-methyl pyrrolidone, and ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 3 grams of 1-METHYLPYRROLIDONEs, then add the Graphene slurry that mass concentration obtained in 2g previous step is 5%, stir.Add 3.7g lithium titanate negative active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on Copper Foil, dries under 100 DEG C of vacuum, after roll-in, make negative plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 0.1C, capacity is 161mAh/g, 1C, discharge capacity is 153mAh/g, 10C, discharge capacity is 131mAh/g.
Embodiment 21
Taking 1g Graphene solid adds in 100gN-methyl pyrrolidone, and ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 3 grams of 1-METHYLPYRROLIDONEs, then add the Graphene slurry that mass concentration obtained in 2g previous step is 5%, stir.Add 3.7g nano-silicon negative active core-shell material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on Copper Foil, dries under 100 DEG C of vacuum, after roll-in, make negative plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.Specific capacity when specific capacity is 1790mAh/g, 500mA/g current density when recording 50mA/g current density is 1231mAh/g.
Embodiment 22
Take 1g polyvinyl alcohol, be dissolved in 100g water, add 1g Graphene solid subsequently, ultrasonic process obtains homodisperse graphene sol in 15 minutes.Adopt and centrifugal above-mentioned graphene sol is concentrated into the slurry that Graphene mass concentration is 5%.
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 3 grams of water, then add the Graphene slurry that mass concentration obtained in 2g previous step is 5%, stir.Add 3.7g modified natural graphite microballoon negative active core-shell material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on Copper Foil, dries under 100 DEG C of vacuum, after roll-in, make negative plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When capacity when recording 0.1C is 357mAh/g, 1C, discharge capacity is 313mAh/g.
Embodiment 23
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid and 2g Super P-Li powder subsequently, first high speed machine is uniformly mixed 10 minutes, more ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 10% (mass percent).
Take 0.2g Kynoar (PVDF) binding agent to be dissolved in 1 gram of 1-METHYLPYRROLIDONE, then to add in 4g previous step obtained mass concentration be the electrocondution slurry of 10%, stir.Add 3.4g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.Gained slurry is spread evenly across on aluminium foil, dries under 100 DEG C of vacuum, after roll-in, make positive plate.With LiPF
6solution is electrolyte, is barrier film, is assembled into lithium ion battery with Cellgard2400.When when recording 1C, discharge capacity is 142mAh/g, 10C, discharge capacity is 107mAh/g, 30C, discharge capacity is 73mAh/g.
Embodiment 24
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid and acetylene black powder subsequently, ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 10% (mass percent).
Subsequent step is identical with embodiment 8.
Embodiment 25
Take 0.2g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 1g Graphene solid and 2g conductive carbon black powder subsequently, first high speed machine is uniformly mixed 10 points and looks for, more ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 10% (mass percent).
Subsequent step is identical with embodiment 8.
Embodiment 26
Take 0.4g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 2g Graphene solid and 1g conductive silver particle subsequently, ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Subsequent step is identical with embodiment 10.
Embodiment 27
Take 0.4g polyvinylpyrrolidone, be dissolved in 100gN-methyl pyrrolidone, add 2g Graphene solid and 1g conductive copper fiber subsequently, ultrasonic process obtains homodisperse colloidal sol in 15 minutes.Adopt and centrifugally above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Subsequent step is identical with embodiment 10.
Claims (9)
1. use a lithium secondary battery preparation method for positive pole negative conductive additive, it is characterized in that carrying out according to the following steps:
(1) by Graphene, or the mixture of Graphene and other electric conducting material adds in water containing dispersant or the first organic solvent, by ultrasonic process or mechanical mixture, or above-mentioned ultrasonic process or mechanical mixture are combined to form homodisperse colloid, the conductive additive slurry concentrated is obtained again by a kind of method in centrifugal, suction filtration or press filtration, further drying removing residual water or the first organic solvent and dispersant, obtain graphene conductive additive agent powder material; (2) graphene conductive additive agent powder and binding agent are scattered in water or the second organic solvent by a certain percentage, after stirring, add cathode plate for lithium secondary battery or negative active core-shell material, dispersed with stirring is to being uniform sizing material, the conventional method prepared according to lithium secondary battery electrode subsequently prepares negative or positive electrode sheet, and be assembled into lithium secondary battery
Wherein, described graphene conductive additive is the mixture of pure Graphene or Graphene and other electric conducting material, in described Graphene and the mixture of other electric conducting material, mass percent shared by Graphene is between 1%-99%, described Graphene is monoatomic layer graphite, or the graphene nanometer sheet of the atom number of plies between 2-15 layer, its lamella lateral dimension is between 0.1-100-μm;
Described dispersant is at least the one in polyvinylpyrrolidone, polyvinyl alcohol, Pluoronic F127, PluoronicP123, Pluronic F68, polyoxyethylene laurel ether, or several combinations;
Described binding agent is Kynoar, or the one in polytetrafluoroethylene, in polyvinyl alcohol, sodium carboxymethylcellulose, methylcellulose, hydroxypropyl methylcellulose, carboxymethyl hydroxyethyl cellulose or hydroxypropyl cellulose, the mass percent of binding agent in cathode plate for lithium secondary battery or negative pole is 1%-10%;
The second described organic solvent be 1-METHYLPYRROLIDONE, ethanol or, acetone, pyridine, aniline, pentamethylene, cyclohexane, normal-butyl ring penta cycloalkanes, 2,2-dimethylhexane, 2, the combination of one or more in 3-dimethylhexane, 2,4-dimethyl pentanes, five methylheptane;
The quality of Graphene contained in graphene conductive additive agent powder or the mass ratio of the gross mass of Graphene and other electric conducting material mixture and binding agent are 0.1 ~ 10: 1;
Graphene quality contained in graphene conductive additive agent powder or the gross mass of Graphene and other electric conducting material mixture, adding the quality sum of binding agent, is 1: 3 ~ 50 with the mass ratio of the second organic solvent.
2. lithium secondary battery preparation method according to claim 1, is characterized in that lithium secondary battery positive active material comprises LiFePO4, lithium ferric manganese phosphate, cobalt acid lithium, spinel lithium manganate, layered lithium manganate, stratiform lithium nickel cobalt dioxide, spinel nickel LiMn2O4, the rich lithium nickel ion doped of stratiform, stratiform cobalt nickel lithium manganate ternary material or lithium vanadate; Lithium secondary battery anode active material comprises flaky graphite, modified natural graphite microballoon, artificial graphite microspheres, carbonaceous mesophase spherules, lithium titanate, nano-silicon or Si-C composite material.
3. lithium secondary battery preparation method according to claim 1, it is characterized in that the addition of graphene conductive additive in cathode plate for lithium secondary battery is 0.5%-30%, mass percentage, calculates according to the solid masses of the mixture of Graphene or Graphene and other electric conducting material; The addition of graphene conductive additive in lithium secondary battery anode is 0.5%-10%, mass percentage, calculates according to the solid masses of Graphene or Graphene and acetylene black mixture.
4. lithium secondary battery preparation method according to claim 1, it is characterized in that other described electric conducting material is at least the one in electrically conductive graphite, conductive carbon black, acetylene black, Super P-Li, carbon nano-tube (CNTs), carbon nano-fiber (VGCF), conductive silver particle, conductive copper particle, conductive aluminum particle, conductive silver fiber, conductive copper fiber, conductive aluminum fiber, or several combinations.
5. the lithium secondary battery preparation method according to claim 1 or 4, it is characterized in that the first described organic solvent be 1-METHYLPYRROLIDONE, ethanol or, acetone, pyridine, aniline, pentamethylene, cyclohexane, normal-butyl ring penta cycloalkanes, 2,2-dimethylhexane, 2, the combination of one or more in 3-dimethylhexane, 2,4-dimethyl pentanes, five methylheptane.
6. lithium secondary battery preparation method according to claim 1, is characterized in that mechanical mixture adopts the one in high-energy stirring, high speed shear or sand milling for liquid phase.
7. lithium secondary battery preparation method according to claim 1, is characterized in that ultrasonic process adopts probe type ultrasonic equipment or ultrasonic cleaning machine, power 100-3000W, ultrasonic time 5-60 minute.
8. lithium secondary battery preparation method according to claim 1, is characterized in that the dry one adopted in constant pressure and dry, vacuumize, spraying dry or freeze drying.
9. the positive pole negative conductive additive for lithium secondary battery, it is characterized in that adopting graphene conductive additive, for the mixture of pure Graphene or Graphene and other electric conducting material, in described Graphene and the mixture of other electric conducting material, the mass percent shared by Graphene is between 1%-99%;
Described graphene conductive additive is powder; Described graphene conductive additive agent powder is by following preparation method: by Graphene, or the mixture of Graphene and other electric conducting material adds in water containing dispersant or organic solvent, by ultrasonic process or mechanical mixture, or above-mentioned ultrasonic process or mechanical mixture are combined to form homodisperse colloid, the conductive additive slurry concentrated is obtained again by a kind of method in centrifugal, suction filtration or press filtration, further drying removing residual water or organic solvent and dispersant, obtain graphene conductive additive agent powder material;
Described Graphene is monoatomic layer graphite, or the graphene nanometer sheet of the atom number of plies between 2-15 layer, and its lamella lateral dimension is between 0.1-100 μm; Described dispersant is at least the one in polyvinylpyrrolidone, polyvinyl alcohol, Pluoronic F127, Pluoronic P123, Pluronic F68, polyoxyethylene laurel ether, or several combinations.
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