CN102544502A - 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 the energy storage material field, be specifically related to a kind of conductive additive that is used for lithium secondary battery and preparation method thereof and relevant battery technology field.
Background technology
Since the beginning of the nineties in last century, first commercialization lithium secondary battery product came out, lithium secondary battery had just obtained to use widely in portable type electronic product because of its high power capacity, high voltage platform, long-life and high security.The problem that concerns survival and development of mankind along with fossil energy exhaustion and global warming etc. becomes increasingly conspicuous, and people constantly enlarge for the demand of clean energy resource, and consequent new forms of energy industry has very huge development prospect and market scale.People expect that generally lithium secondary battery will fully develop talents in this industry, especially be that the application prospect in the electrokinetic cell of representative has attracted global sight especially at large-scale energy storage device with the electric automobile.For this reason, countries in the world have all been dropped into lot of manpower and material resources and have been carried out the research and development of novel high-performance lithium secondary battery, to satisfy the higher requirement that large-sized power battery and energy-storage battery propose at aspects such as energy density, power density, cycle life and fail safes.
A kind of as battery, lithium secondary battery requires its electrode to have good electrical conductivity naturally.The conductivity of positive electrode active materials such as LiFePO4 commonly used at present, LiMn2O4, ternary material itself all is not very high, has big contact resistance simultaneously between the positive electrode particle.Therefore, in positive pole preparation, all need add additive to improve the electron transfer rate in anodal with high conductivity.The graphite-like active material of using always in the negative pole; Though itself has good electrical conductivity; But in order to overcome intergranular contact resistance; Especially in the time of will realizing big multiplying power discharging, still need improve its conductivity through adding conductive agent, the ability that makes its electron conduction ability and lithium ion from graphite, take off embedding reaches to balance.Therefore, conductive additive plays an important role in lithium secondary battery, also is an indispensable part of this industry.
At present, commercial conductive agent is main with material with carbon element, mainly comprises electrically conductive graphite, acetylene black, Super P-Li etc. and the high-end carbon nanotube conducting additive of low side.Though the former low price is difficult to satisfy battery continuing under high magnification and discharges and recharges; Although latter's performance is outstanding, be particularly useful for high-power battery, the price limit that it is expensive its practical application in lithium secondary battery.Therefore, the high-performance conductive additive of development of new cheapness is very urgent.
Graphene is one type of new carbon finding in 2004, and it has unique two-dimensional nanostructure and novel physical chemical property, has therefore received the extensive concern of scientific circles and industrial circle, and 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 both had been different from three-dimensional conductive particles such as electrically conductive graphite or Super P-Li, also was different from the CNT of one dimension.Be easy to be wrapped in around the electrode active material particles like the Graphene of " pliable and tough " as the film, the contact of formation face, and be easy to form three-dimensional conductive network.On the other hand, the Graphene good heat-conducting also benefits for the lifting of battery high-temperature behavior and cyclical stability.Before us, in the national inventing patent (application number 201010514810.0) of application,, can realize the mass preparation of high-quality Graphene through improved method, and (significantly being lower than CNT) with low cost.Therefore, the graphene conductive additive has remarkable advantages than other conductive agent products.
Summary of the invention
Primary technical problem to be solved by this invention is to the above-mentioned state of the art a kind of anodal negative pole conductive additive that is used for lithium secondary battery to be provided; It realizes the fast transferring of electronics in electrode; Be beneficial to high power charging-discharging, can promote the high-temperature behavior and the cycle life of battery simultaneously.
Another technical problem to be solved by this invention is to the above-mentioned state of the art a kind of preparation method who is used for the anodal negative pole conductive additive of lithium secondary battery to be provided, and its method is simple, implements easily.
Another technical problem to be solved by this invention is the preparation method that a kind of relevant lithium secondary battery is provided to the above-mentioned state of the art.
The technical scheme that the present invention is adopted for the above-mentioned primary technical problem of solution is: a kind of anodal negative pole conductive additive that is used for lithium secondary battery; It is characterized in that adopting the graphene conductive additive; Mixture for pure Graphene or Graphene and other electric conducting material; In the mixture of described Graphene and other electric conducting material, the shared mass percent of Graphene is between 1%-99%.
As improvement; Described graphene conductive additive is a powder; Perhaps for being scattered in the graphene conductive additive slurry in water or the organic solvent; Perhaps for being scattered in the water that contains dispersant or the graphene conductive additive slurry in the organic solvent; The mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30% in the described graphene conductive additive slurry, and the quality percentage composition of described dispersant in the graphene conductive additive slurry is 0.1%-10%.
Preferably, described Graphene is a monoatomic layer graphite, or the graphene nanometer sheet of the atom number of plies between the 2-15 layer, and its lamella lateral dimension is between 0.1-100 μ m.
Preferably; Described other electric conducting material is at least a kind of in electrically conductive graphite, conductive carbon black, acetylene black, Super P-Li, CNT (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, the conductive aluminum fiber or several kinds combination.
Preferably; Described organic solvent is N-methyl pyrrolidone, ethanol, acetone, pyridine, aniline, pentamethylene, cyclohexane, normal-butyl ring penta cycloalkanes, 2; 2-dimethylhexane, 2,3-dimethylhexane, 2, the combination of one or more in 4-dimethyl pentane, the five methylheptane.
Preferably, described dispersant is at least a kind of in polyvinylpyrrolidone, polyvinyl alcohol, Pluoronic F127, Pluoronic P123, Pluronic F68, the polyoxyethylene laurel ether or several kinds combination.
The technical scheme that the present invention is adopted for above-mentioned another technical problem of solution is: a kind of preparation method who is used for the anodal negative pole conductive additive of lithium secondary battery is characterized in that this method selects to carry out by following step separately:
1) the graphene conductive additive agent powder is through a kind of preparation of following two kinds of methods:
A) Graphene powder and other electric conducting material powder are obtained the compound powder through mechanical mixture, make the mixture of described Graphene and other electric conducting material, the shared mass percent of its Graphene is between 1%-99%;
Or,
B) be with Graphene; Perhaps the mixture of Graphene and other electric conducting material adds entry or organic solvent; Or with Graphene, perhaps the adding of the mixture of Graphene and other electric conducting material contains in the water or organic solvent of dispersant, through sonicated or mechanical mixture; Or above-mentioned sonicated or mechanical mixture are combined to form homodisperse colloid; The conductive additive slurry that obtains concentrating through a kind of method in centrifugal, suction filtration or the press filtration again, further drying is removed residual water or solvent and dispersant, obtains graphene conductive additive agent powder material; Make the mixture of described Graphene and other electric conducting material, the shared mass percent of its Graphene is between 1%-99%;
2) the conductive additive slurry that is scattered in water or the organic solvent prepares through following method:
With Graphene; Perhaps the mixture of Graphene and other electric conducting material adds in entry or the organic solvent; In the mixture of described Graphene and other electric conducting material; The shared mass percent of Graphene between 1%-99%, through sonicated or mechanical mixture, perhaps above-mentioned sonicated or mechanical mixing be combined to form homodisperse colloid; Obtain the conductive additive slurry after concentrating through a kind of method in centrifugal, suction filtration or the press filtration, the mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30% in the described graphene conductive additive slurry again;
3) being scattered in the water that contains dispersant or the graphene conductive additive slurry in the organic solvent prepares through following method:
Earlier dispersant is dissolved in water or the organic solvent; Add Graphene subsequently; The perhaps mixture of Graphene and other electric conducting material; In the mixture of described Graphene and other electric conducting material, the shared mass percent of Graphene is between 1%-99%, through sonicated or mechanical mixture; Or this above-mentioned sonicated or mechanical mixture be combined to form homodisperse colloid; Obtain the conductive additive slurry after concentrating through a kind of method in centrifugal, suction filtration or the press filtration, the mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30% in the described graphene conductive additive slurry again, and the quality percentage composition of described dispersant in the graphene conductive additive slurry is 0.1%-10%.
Preferably, mechanical mixture adopts a kind of in ball milling, sand milling or the dry stirring for powder.
Preferably, mechanical mixture adopts a kind of in high-energy stirring, high speed shear or the sand milling for liquid phase.
Preferably, sonicated adopts probe type ultrasonic equipment or ultrasonic cleaning machine, power 100-3000W, ultrasonic time 5-60 minute.
Preferably, dryly adopt a kind of in constant pressure and dry, vacuumize, spray drying or the freeze drying.
The technical scheme that the present invention is adopted for above-mentioned another technical problem of solution is: a kind of lithium secondary battery preparation method who uses anodal negative pole conductive additive 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 the 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 to and is uniform sizing material, and the conventional method according to the lithium secondary battery electrode preparation prepares the negative or positive electrode sheet subsequently, and is assembled into lithium secondary battery;
When said graphene conductive additive adopts powder, be the mixture of pure Graphene or Graphene and other electric conducting material, in the mixture of described Graphene and other electric conducting material, the shared mass percent of Graphene is between 1%-99%; When adopting slurry; For being scattered in the graphene conductive additive slurry in water or the organic solvent; Perhaps for being scattered in the water that contains dispersant or the graphene conductive additive slurry in the organic solvent; The mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30% in the described graphene conductive additive slurry, and the quality percentage composition of described dispersant in the graphene conductive additive slurry is 0.1%-10%;
Described binding agent is a Kynoar; Or a kind of in the polytetrafluoroethylene, in polyvinyl alcohol, sodium carboxymethylcellulose, methylcellulose, hydroxypropyl methylcellulose, carboxymethyl hydroxyethyl cellulose or the 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 N-methyl pyrrolidone, ethanol or, acetone, pyridine, aniline, pentamethylene, cyclohexane, normal-butyl ring penta cycloalkanes, 2; 2-dimethylhexane, 2; 3-dimethylhexane, 2, the combination of one or more in 4-dimethyl pentane, the five methylheptane.
The mass ratio of the gross mass of the quality of contained Graphene or Graphene and other electric conducting material mixture and binding agent is 0.1～10: 1 in graphene conductive additive agent powder or the slurry.
The contained Graphene quality or the gross mass of Graphene and other electric conducting material mixture in graphene conductive additive agent powder or the slurry add the quality sum of binding agent, with the mass ratio of organic solvent be 1: 3～50.
Preferably, lithium secondary battery positive active material comprises LiFePO4, phosphoric acid ferrimanganic lithium, cobalt acid lithium, spinel lithium manganate, layered lithium manganate, stratiform lithium nickel cobalt dioxide, spinelle nickel LiMn2O4, the rich lithium nickel of stratiform LiMn2O4, stratiform nickle cobalt lithium manganate ternary material or lithium vanadate; The 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%, and the quality percentage composition 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%, and the quality percentage composition is according to the solid masses calculating of Graphene or Graphene and acetylene black mixture.
Compared with prior art; The invention has the advantages that: compare with present commercial electrically conductive graphite, conductive carbon black, Super P-Li and carbon nanotube conducting additive; Graphene not only has high conductivity; And its unique two-dimensional nanostructure can form the three-dimensional conductive network that is wrapped in around the both positive and negative polarity active material very effectively; Two dimension is laminar structured simultaneously can closely contact with electrode active material with the mode of face contact, thereby realizes the fast transferring of electronics in electrode, is beneficial to high power charging-discharging.Simultaneously, the thermal conductivity that Graphene is good has positive meaning for the heat that produces in the quick conduction charge and discharge process, can promote the high-temperature behavior and the cycle life of battery.In addition, the specific area that Graphene is huge also helps the raising of battery performance for electrolyte good adsorption and maintenance effect.It is pointed out that also with high-end CNT and compare that the preparation cost of Graphene is lower, therefore in practical application, have more advantage.Through using the charge-discharge performance test result of carrying out after the graphene conductive agent to show to multiple different lithium anode of secondary battery, negative pole system; The graphene conductive additive is obvious for the castering action of battery high rate performance; And be superior to present commercial conductive additive; Be a superior performance, and have the novel conductive additive product of great market prospect.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of the lithium iron phosphate positive material of interpolation graphene conductive agent.
The discharge curve of Fig. 2 a, 2b (right side) battery during for the graphene conductive additive (left side) that in identical lithium iron phosphate positive material, adds same quality percentage composition (15%) respectively and Super P-Li conductive additive.The result shows that the graphene conductive additive obviously is superior to 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 by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 5 gram N-methyl pyrrolidones, add 0.6g Graphene powder conductive additive again, stir.Add the 3.2g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 142mAh/g when recording 1C, and discharge capacity is 110mAh/g during 10C, and discharge capacity is 80mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 2
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 5 gram N-methyl pyrrolidones, add 0.2g Graphene powder conductive additive again, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 140mAh/g when recording 1C, and discharge capacity is 100mAh/g during 10C, and discharge capacity is 60mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 3
Take by weighing 1g Graphene solid and add in the 100gN-methyl pyrrolidone, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 140mAh/g when recording 1C, and discharge capacity is 105mAh/g during 10C, and discharge capacity is 69mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 4
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 141mAh/g when recording 1C, and discharge capacity is 103mAh/g during 10C, and discharge capacity is 66mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 5
Take by weighing 0.2g Pluoronic P123, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 141mAh/g when recording 1C, and discharge capacity is 104mAh/g during 10C, and discharge capacity is 65mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 6
Take by weighing the 0.2g polyvinyl alcohol, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 142mAh/g when recording 1C, and discharge capacity is 102mAh/g during 10C, and discharge capacity is 66mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 7
Take by weighing the 0.2g polyoxyethylene laurel ether, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 141mAh/g when recording 1C, and discharge capacity is 103mAh/g during 10C, and discharge capacity is 66mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 8
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid and 2g Super P-Li powder subsequently, sonicated obtained homodisperse colloidal sol in 15 minutes.Adopt and centrifugal above-mentioned colloidal sol is concentrated into the slurry that solid content is 10% (mass percent).
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 10% electrocondution slurry, stir.Add the 3.4g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 141mAh/g when recording 1C, and discharge capacity is 108mAh/g during 10C, and discharge capacity is 76mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 9
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid and 2g acetylene black powder subsequently, sonicated obtained homodisperse colloidal sol in 15 minutes.Adopt and centrifugal above-mentioned colloidal sol is concentrated into the slurry that solid content is 10% (mass percent).
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 10% electrocondution slurry, stir.Add the 3.4g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 140mAh/g when recording 1C, and discharge capacity is 109mAh/g during 10C, and discharge capacity is 78mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 10
Take by weighing the 0.4g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 2g Graphene solid and 1g CNT subsequently, sonicated obtained homodisperse colloidal sol in 15 minutes.Adopt and centrifugal above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% electrocondution slurry, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 143mAh/g when recording 1C, and discharge capacity is 112mAh/g during 10C, and discharge capacity is 81mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 11
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid, 1g acetylene black and 1g CNT subsequently, sonicated obtained homodisperse colloidal sol in 15 minutes.Adopt and centrifugal above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% electrocondution slurry, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 141mAh/g when recording 1C, and discharge capacity is 107mAh/g during 10C, and discharge capacity is 73mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 12
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid and 1.5g acetylene black and 0.5g conductive silver particle subsequently, sonicated obtained homodisperse colloidal sol in 15 minutes.Adopt and centrifugal above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% electrocondution slurry, stir.Add the 3.6g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 140mAh/g when recording 1C, and discharge capacity is 111mAh/g during 10C, and discharge capacity is 77mAh/g during 30C.After the charge and discharge cycles 500 times, capacity attenuation is less than 5% under 1C for battery.
Embodiment 13
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.6g lithium cobaltate cathode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 145mAh/g when recording 0.1C, and discharge capacity is 138mAh/g during 1C.
Embodiment 14
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.6g spinel lithium manganese oxide anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 132mAh/g when recording 0.1C, and discharge capacity is 111mAh/g during 1C.
Embodiment 15
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.6g lithium nickel cobalt dioxide positive electrode active materials subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 175mAh/g when recording 0.1C, and discharge capacity is 155mAh/g during 1C.
Embodiment 16
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.6g nickle cobalt lithium manganate tertiary cathode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 188mAh/g when recording 0.1C, and discharge capacity is 169mAh/g during 1C.
Embodiment 17
Take by weighing 1g Graphene solid and add in the 100gN-methyl pyrrolidone, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 3 gram N-methyl pyrrolidones, add mass concentration that 2g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.7g modified natural graphite microballoon negative active core-shell material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the Copper Foil, under 100 ℃ of vacuum, dried, process negative plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Capacity is 355mAh/g when recording 0.1C, and capacity is 315mAh/g during 1C.
Embodiment 18
Take by weighing the 1g polyvinylpyrrolidone, be dissolved in the 100g water, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 3 gram water, add mass concentration that 2g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.7g modified natural graphite microballoon negative active core-shell material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the Copper Foil, under 100 ℃ of vacuum, dried, process negative plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Capacity is 353mAh/g when recording 0.1C, and capacity is 311mAh/g during 1C.
Embodiment 19
Take by weighing 1g Graphene solid and add in the 100gN-methyl pyrrolidone, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 3 gram N-methyl pyrrolidones, add mass concentration that 2g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.7g carbonaceous mesophase spherules negative active core-shell material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the Copper Foil, under 100 ℃ of vacuum, dried, process negative plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Capacity is 359mAh/g when recording 0.1C, and capacity is 317mAh/g during 1C.
Take by weighing 1g Graphene solid and add in the 100gN-methyl pyrrolidone, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 3 gram N-methyl pyrrolidones, add mass concentration that 2g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.7g lithium titanate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the Copper Foil, under 100 ℃ of vacuum, dried, process negative plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Capacity is 161mAh/g when recording 0.1C, and discharge capacity is 153mAh/g during 1C, and discharge capacity is 131mAh/g during 10C.
Embodiment 21
Take by weighing 1g Graphene solid and add in the 100gN-methyl pyrrolidone, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 3 gram N-methyl pyrrolidones, add mass concentration that 2g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.7g nano-silicon negative active core-shell material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the Copper Foil, under 100 ℃ of vacuum, dried, process negative plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Specific capacity is 1790mAh/g when recording the 50mA/g current density, and the specific capacity during the 500mA/g current density is 1231mAh/g.
Embodiment 22
Take by weighing the 1g polyvinyl alcohol, be dissolved in the 100g water, add 1g Graphene solid subsequently, sonicated obtained homodisperse Graphene colloidal sol in 15 minutes.Adopt that centrifugal above-mentioned Graphene colloidal sol is concentrated into the Graphene mass concentration is 5% slurry.
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 3 gram water, add mass concentration that 2g last makes in going on foot again and be 5% Graphene slurry, stir.Add 3.7g modified natural graphite microballoon negative active core-shell material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the Copper Foil, under 100 ℃ of vacuum, dried, process negative plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Capacity when recording 0.1C is 357mAh/g, and discharge capacity is 313mAh/g during 1C.
Embodiment 23
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid and 2g Super P-Li powder subsequently, first high speed machine mixed 10 minutes, and sonicated obtained homodisperse colloidal sol in 15 minutes again.Adopt and centrifugal above-mentioned colloidal sol is concentrated into the slurry that solid content is 10% (mass percent).
Take by weighing 0.2g Kynoar (PVDF) binding agent and be dissolved in the 1 gram N-methyl pyrrolidone, add mass concentration that 4g last makes in going on foot again and be 10% electrocondution slurry, stir.Add the 3.4g lithium iron phosphate anode active material subsequently, dispersed with stirring 1 hour.The gained slurry is evenly coated on the aluminium foil, under 100 ℃ of vacuum, dried, process positive plate after the roll-in.With LiPF
6Solution is electrolyte, is barrier film with Cellgard2400, is assembled into lithium ion battery.Discharge capacity is 142mAh/g when recording 1C, and discharge capacity is 107mAh/g during 10C, and discharge capacity is 73mAh/g during 30C.
Embodiment 24
Take by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid and acetylene black powder subsequently, sonicated obtained homodisperse colloidal sol in 15 minutes.Adopt and centrifugal 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 by weighing the 0.2g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 1g Graphene solid and 2g conductive carbon black powder subsequently, first high speed machine mixes to be looked in 10 minutes, and sonicated obtained homodisperse colloidal sol in 15 minutes again.Adopt and centrifugal 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 by weighing the 0.4g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 2g Graphene solid and 1g conductive silver particle subsequently, sonicated obtained homodisperse colloidal sol in 15 minutes.Adopt and centrifugal 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 by weighing the 0.4g polyvinylpyrrolidone, be dissolved in the 100gN-methyl pyrrolidone, add 2g Graphene solid and 1g conductive copper fiber subsequently, sonicated obtained homodisperse colloidal sol in 15 minutes.Adopt and centrifugal above-mentioned colloidal sol is concentrated into the slurry that solid content is 5% (mass percent).
Subsequent step is identical with embodiment 10.
Claims (14)
1. anodal negative pole conductive additive that is used for lithium secondary battery; It is characterized in that adopting the graphene conductive additive; Mixture for pure Graphene or Graphene and other electric conducting material; In the mixture of described Graphene and other electric conducting material, the shared mass percent of Graphene is between 1%-99%.
2. the anodal negative pole conductive additive that is used for lithium secondary battery according to claim 1; It is characterized in that: described graphene conductive additive is a powder; Perhaps for being scattered in the graphene conductive additive slurry in water or the organic solvent; Perhaps for being scattered in the water that contains dispersant or the graphene conductive additive slurry in the organic solvent; The mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30% in the described graphene conductive additive slurry, and the quality percentage composition of described dispersant in the graphene conductive additive slurry is 0.1%-10%.
3. according to the anodal negative pole conductive additive that is used for lithium secondary battery described in the claim 2; It is characterized in that: described Graphene is a monoatomic layer graphite; Or the graphene nanometer sheet of the atom number of plies between the 2-15 layer, its lamella lateral dimension is between 0.1-100 μ m.
4. according to claim 2 or the described anodal negative pole conductive additive that is used for lithium secondary battery of 3 claims; It is characterized in that: described other electric conducting material is at least a kind of in electrically conductive graphite, conductive carbon black, acetylene black, Super P-Li, CNT (CNTs), carbon nano-fiber (VGCF), conductive silver particle, conductive copper particle, conductive aluminum particle, conductive silver fiber, conductive copper fiber, the conductive aluminum fiber or several kinds combination.
5. according to claim 2 or the described anodal negative pole conductive additive that is used for lithium secondary battery of 3 claims; It is characterized in that: described organic solvent be N-methyl pyrrolidone, ethanol or, acetone, pyridine, aniline, pentamethylene, cyclohexane, normal-butyl ring penta cycloalkanes, 2; 2-dimethylhexane, 2; 3-dimethylhexane, 2, the combination of one or more in 4-dimethyl pentane, the five methylheptane.
6. according to claim 2 or the described anodal negative pole conductive additive that is used for lithium secondary battery of 3 claims; It is characterized in that: described dispersant is at least a kind of in polyvinylpyrrolidone, polyvinyl alcohol, Pluoronic F127, Pluoronic P123, Pluronic F68, the polyoxyethylene laurel ether or several kinds combination.
7. preparation method who is used for the anodal negative pole conductive additive of lithium secondary battery is characterized in that this method selects to carry out by following step separately:
(1) the graphene conductive additive agent powder is through a kind of preparation of following two kinds of methods:
Graphene powder and other electric conducting material powder are obtained the compound powder through mechanical mixture, make the mixture of described Graphene and other electric conducting material, the shared mass percent of its Graphene is between 1%-99%;
Or,
Be with Graphene; Perhaps the mixture of Graphene and other electric conducting material adds entry or organic solvent; Or with Graphene, perhaps the adding of the mixture of Graphene and other electric conducting material contains in the water or organic solvent of dispersant, through sonicated or mechanical mixture; Or above-mentioned sonicated or mechanical mixture are combined to form homodisperse colloid; The conductive additive slurry that obtains concentrating through a kind of method in centrifugal, suction filtration or the press filtration again, further drying is removed residual water or solvent and dispersant, obtains graphene conductive additive agent powder material; Make the mixture of described Graphene and other electric conducting material, the shared mass percent of its Graphene is between 1%-99%;
(2) the conductive additive slurry that is scattered in water or the organic solvent prepares through following method:
With Graphene; Perhaps the mixture of Graphene and other electric conducting material adds in entry or the organic solvent; In the mixture of described Graphene and other electric conducting material; The shared mass percent of Graphene between 1%-99%, through sonicated or mechanical mixture, perhaps above-mentioned sonicated or mechanical mixing be combined to form homodisperse colloid; Obtain the conductive additive slurry after concentrating through a kind of method in centrifugal, suction filtration or the press filtration, the mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30% in the described graphene conductive additive slurry again;
(3) being scattered in the water that contains dispersant or the graphene conductive additive slurry in the organic solvent prepares through following method:
Earlier dispersant is dissolved in water or the organic solvent; Add Graphene subsequently; The perhaps mixture of Graphene and other electric conducting material; In the mixture of described Graphene and other electric conducting material, the shared mass percent of Graphene is between 1%-99%, through sonicated or mechanical mixture; Or this above-mentioned sonicated or mechanical mixture be combined to form homodisperse colloid; Obtain the conductive additive slurry after concentrating through a kind of method in centrifugal, suction filtration or the press filtration, the mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30% in the described graphene conductive additive slurry again, and the quality percentage composition of described dispersant in the graphene conductive additive slurry is 0.1%-10%.
8. preparation method according to claim 7 is characterized in that mechanical mixture adopts a kind of in ball milling, sand milling or the dry stirring for powder.
9. preparation method according to claim 7 is characterized in that mechanical mixture adopts a kind of in high-energy stirring, high speed shear or the sand milling for liquid phase.
10. preparation method according to claim 7 is characterized in that sonicated adopts probe type ultrasonic equipment or ultrasonic cleaning machine, power 100-3000W, ultrasonic time 5-60 minute.
11. preparation method according to claim 7 is characterized in that dry a kind of in constant pressure and dry, vacuumize, spray drying or the freeze drying of adopting.
12. a lithium secondary battery preparation method who uses anodal negative pole conductive additive 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 the 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, and the conventional method according to the lithium secondary battery electrode preparation prepares the negative or positive electrode sheet subsequently, and is assembled into lithium secondary battery;
When said graphene conductive additive adopts powder, be the mixture of pure Graphene or Graphene and other electric conducting material, in the mixture of described Graphene and other electric conducting material, the shared mass percent of Graphene is between 1%-99%; When adopting slurry; For being scattered in the graphene conductive additive slurry in water or the organic solvent; Perhaps for being scattered in the water that contains dispersant or the graphene conductive additive slurry in the organic solvent; The mass percent of the mixture of Graphene or Graphene and other electric conducting material is 0.5%-30% in the described graphene conductive additive slurry, and the quality percentage composition of described dispersant in the graphene conductive additive slurry is 0.1%-10%;
Described binding agent is a Kynoar; Or a kind of in the polytetrafluoroethylene, in polyvinyl alcohol, sodium carboxymethylcellulose, methylcellulose, hydroxypropyl methylcellulose, carboxymethyl hydroxyethyl cellulose or the 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 N-methyl pyrrolidone, ethanol or, acetone, pyridine, aniline, pentamethylene, cyclohexane, normal-butyl ring penta cycloalkanes, 2; 2-dimethylhexane, 2; 3-dimethylhexane, 2, the combination of one or more in 4-dimethyl pentane, the five methylheptane.
The mass ratio of the gross mass of the quality of contained Graphene or Graphene and other electric conducting material mixture and binding agent is 0.1～10: 1 in graphene conductive additive agent powder or the slurry.
The contained Graphene quality or the gross mass of Graphene and other electric conducting material mixture in graphene conductive additive agent powder or the slurry add the quality sum of binding agent, with the mass ratio of organic solvent be 1: 3～50.
13., it is characterized in that lithium secondary battery positive active material comprises LiFePO4, phosphoric acid ferrimanganic lithium, cobalt acid lithium, spinel lithium manganate, layered lithium manganate, stratiform lithium nickel cobalt dioxide, spinelle nickel LiMn2O4, the rich lithium nickel of stratiform LiMn2O4, stratiform nickle cobalt lithium manganate ternary material or lithium vanadate according to the lithium secondary battery preparation method of claim 12; The 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.
14. lithium secondary battery preparation method according to claim 12; It is characterized in that the addition of graphene conductive additive in cathode plate for lithium secondary battery is 0.5%-30%; The quality percentage composition 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%, and the quality percentage composition is according to the solid masses calculating of Graphene or Graphene and acetylene black mixture.
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| CN114899369A (en) * | 2022-04-08 | 2022-08-12 | 西部诚业科技发展(深圳)有限公司 | Conductive composition and preparation method thereof |
| CN114899369B (en) * | 2022-04-08 | 2024-03-12 | 西部诚业科技发展(深圳)有限公司 | Conductive composition and preparation method thereof |
| CN116532017A (en) * | 2023-04-21 | 2023-08-04 | 盐城工学院 | Homogenization method of battery anode material |
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