CN105576185A - Silicon-carbon composite cathode pole piece of lithium ion battery and preparation method of silicon-carbon composite cathode pole piece - Google Patents

Silicon-carbon composite cathode pole piece of lithium ion battery and preparation method of silicon-carbon composite cathode pole piece Download PDF

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Publication number
CN105576185A
CN105576185A CN201610154249.7A CN201610154249A CN105576185A CN 105576185 A CN105576185 A CN 105576185A CN 201610154249 A CN201610154249 A CN 201610154249A CN 105576185 A CN105576185 A CN 105576185A
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silicon
carbon
pole piece
cathode pole
composite cathode
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赵家兴
孔令丽
张克军
孙杰
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Tianjin Lishen Battery JSCL
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Tianjin Lishen Battery JSCL
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a silicon-carbon composite cathode pole piece of a lithium ion battery. The silicon-carbon composite cathode pole piece comprises a cathode current collector, wherein one silicon-carbon cathode active material layer coats the surface of the cathode current collector; the silicon-carbon cathode active material layer is prepared from the following components by mass percent: 80%-99.5% of a silicon-carbon composite material, 0%-15% of a graphene conductive agent, 0%-15% of a carbon nano tube conductive agent, 0%-15% of a carbon black conductive agent and 0.2%-20% of a binding agent. Furthermore, the invention discloses a preparation method of the silicon-carbon composite cathode pole piece. According to the silicon-carbon composite cathode pole piece and the preparation method of the silicon-carbon composite cathode pole piece, disclosed by the invention, the silicon-carbon composite cathode pole piece can be used for effectively improving the conductive property of a silicon-based material and guaranteeing low impedance and long cycle life of the lithium ion battery applied by the cathode pole piece; the whole properties of the lithium ion battery are greatly improved, and long-time use requirements of electronic products can be met; and a market application prospect of products of battery manufacturers can be improved easily.

Description

Silicon-carbon composite cathode pole piece of a kind of lithium ion battery and preparation method thereof
Technical field
The present invention relates to cell art, silicon-carbon composite cathode pole piece particularly relating to a kind of lithium ion battery and preparation method thereof.
Background technology
At present, lithium ion battery is current internationally recognized desirable chemical power supply, there is the many merits such as voltage is high, energy density large, have extended cycle life, self discharge is little, memory-less effect, operating temperature range are wide, pollution-free, be widely used in mobile phone, laptop computer, portable power tool, weaponry etc.
The development of green energy resource technology and low-carbon economy, commercial Li-ion battery is more and more subject to global attention.In recent years, the swift and violent progress of electric motor car and consumer electronics product, the demand for the lithium ion battery with high energy density with more permanent flying power is very urgent.
Wherein, in negative material, current business-like lithium ion battery mainly adopts graphite-like carbon negative pole material, and its electric conductivity is excellent, cyclical stability is high, but the theoretical gram volume of its 372mAh/g can not meet the widespread demand to lithium ion battery with high energy density.Therefore, a large amount of technical research has turned to finds novel height theoretical gram volume negative pole system.At present, although the theoretical gram volume of the embedding lithium of silicon is up to 4200mAh/g, and reserves are on earth very abundant, have great application prospect.But, silica-base material because its volumetric expansion is large, poor electric conductivity and poor cycle performance limit its practical application.Be in particular in: the volumetric expansion of silicon materials causes the contact force between silicon materials and between silicon materials and conductive agent to reduce, cause the cyclical stability of battery poor, and the poor electric conductivity of silicon materials itself, cause the increase of battery impedance, reduce the cycle performance of battery.
In recent years, vast scientific research personnel and battery operated person have carried out large quantifier elimination around silica-base material.But existing technical staff is about the research of silica-base material is mainly in the expansion suppressing cathode pole piece, and cannot improve the electric conductivity of silica-base material, the battery prepared by silica-base material still has the problem that impedance is high, cycle life is shorter.
Therefore, at present in the urgent need to developing a kind of technology, it effectively can improve the electric conductivity of silica-base material, ensures that the lithium ion battery impedance that the cathode pole piece prepared by silica-base material is applied is low, has extended cycle life, increase substantially the overall performance of lithium ion battery.
Summary of the invention
In view of this, silicon-carbon composite cathode pole piece that the object of this invention is to provide a kind of lithium ion battery and preparation method thereof, this silicon-carbon composite cathode pole piece effectively can improve the electric conductivity of silica-base material, ensure that the lithium ion battery impedance that cathode pole piece is applied is low, have extended cycle life, increase substantially the overall performance of lithium ion battery, the long user demand of electronic product can be met, be conducive to the market application foreground improving cell production companies product, be of great practical significance.
For this reason, the invention provides a kind of silicon-carbon composite cathode pole piece of lithium ion battery, comprise negative current collector, the surface-coated of shown negative current collector has one deck silicon-carbon cathode active material layer;
Described silicon-carbon cathode active material layer comprise mass percent be 80% ~ 99.5% Si-C composite material, 0% ~ 15% graphene conductive agent, the carbon nanotube conducting agent of 0% ~ 15%, the carbon black conductive agent of 0% ~ 15% and 0.2% ~ 20% binding agent.
Wherein, described negative current collector is Copper Foil or the cated Copper Foil of surperficial tool;
The coating that described copper foil surface has is the coating adopting at least one Material coating in graphite, Graphene, carbon nano-tube, agraphitic carbon, conductive black, acetylene black, conductive black SuperP to be formed.
Wherein, the silicon materials comprised in described Si-C composite material and the mass ratio of material with carbon element are 1:(0.1 ~ 100);
Described silicon materials are nano-silicon, silica, the sub-silicon of oxidation or silicon-containing alloy; Described material with carbon element is hard carbon, soft carbon, native graphite, Delanium or carbonaceous mesophase spherules.
Wherein, described graphene conductive agent comprises at least one in single-layer graphene, multi-layer graphene and modified graphene;
Described carbon nanotube conducting agent comprises at least one in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and modified carbon nano-tube;
Described carbon black conductive agent comprises at least one in graphite, agraphitic carbon, acetylene black and conductive black SuperP;
Described binding agent comprises at least one in carboxyl methyl cellulose, butadiene-styrene rubber, Kynoar, polytetrafluoroethylene, epoxy resin, polyvinyl alcohol, polyimides and polyacrylic acid.
In addition, present invention also offers a kind of preparation method of silicon-carbon composite cathode pole piece of lithium ion battery, comprise the following steps:
The first step, joins in deionized water by carboxyl methyl cellulose powder, and the solid content being formulated to glue is 0.1% ~ 10%, then stirs, and obtains CMC glue;
Second step, joins Graphene, carbon nano-tube and carbon black conductive agent in described carboxyl methyl cellulose glue, then stirs and obtain conducting resinl;
3rd step, adds material with carbon element and silicon materials in described conducting resinl simultaneously, after stirring, adds solid content to 35% ~ 55% of deionized water adjustment conducting resinl, and then stirs and mix, obtain the conducting resinl comprising silicon materials and material with carbon element;
4th step, continued to add butadiene-styrene rubber to described comprising in the conducting resinl of silicon materials and material with carbon element, and stir acquisition slurry;
5th step, filters described for acquisition slurry;
6th step, is coated on negative pole currect collecting surface by the described slurry through filtering, and carries out air blast by the blower fan be put in baking box simultaneously, realize heating, drying, final acquisition silicon-carbon composite cathode pole piece.
Wherein, in a first step, the mass ratio between described carboxyl methyl cellulose powder and deionized water is 1:(10 ~ 1000);
In second step, described Graphene, carbon nano-tube, mass ratio between carbon black conductive agent and CMC glue are: (0 ~ 15): (0 ~ 15): (0 ~ 15): 100;
In the 4th step, described butadiene-styrene rubber and the described mass ratio comprised between silicon materials and the conducting resinl of material with carbon element are 1:(10 ~ 1000).
Wherein, in a first step, 4h ~ 24h is stirred with the mixing speed of 100rpm ~ 800rpm;
In second step, stir 0.5h ~ 2.5h with the mixing speed of 1500rpm ~ 4000rpm;
In the 4th step, stir 10min ~ 30min with the mixing speed of 100rpm ~ 800rpm.
Wherein, described 3rd step is specially: add material with carbon element and silicon materials in described conducting resinl after simultaneously, first stir 15min ~ 60min by the mixing speed of 100rpm ~ 800rpm, then 2h ~ 6h is stirred by the mixing speed of 1500rpm ~ 4000rpm, add solid content to 35% ~ 55% of deionized water adjustment conducting resinl, stir 0.5h ~ 1.5h by the mixing speed of 1500rpm ~ 4000rpm again, obtain the conducting resinl comprising silicon materials and material with carbon element.
Wherein, in the third step, described conducting resinl, material with carbon element, mass ratio between silicon materials and deionized water are (0.01 ~ 100): 1:(0.1 ~ 100): (0.1 ~ 100);
Wherein said silicon materials are nano-silicon, silica, the sub-silicon of oxidation or silicon-containing alloy, and described material with carbon element is hard carbon, soft carbon, native graphite, Delanium or carbonaceous mesophase spherules.
Wherein, described 5th step is specially: filtered by 80 ~ 150 mesh sieves by described for acquisition slurry.
From above technical scheme provided by the invention, compared with prior art, silicon-carbon composite cathode pole piece that the invention provides a kind of lithium ion battery and preparation method thereof, this silicon-carbon composite cathode pole piece effectively can improve the electric conductivity of silica-base material, ensure that the lithium ion battery impedance that cathode pole piece is applied is low, have extended cycle life, increase substantially the overall performance of lithium ion battery, the long user demand of electronic product can be met, be conducive to the market application foreground improving cell production companies product, be of great practical significance.
Accompanying drawing explanation
Fig. 1 is the preparation method of the silicon-carbon composite cathode pole piece using lithium ion battery provided by the invention, at the Electronic Speculum figure of the silicon-carbon composite cathode pole piece that embodiment 1 is made;
Fig. 2 is the preparation method of the silicon-carbon composite cathode pole piece using lithium ion battery provided by the invention, and the silicon-carbon composite cathode sheet made respectively in embodiment 1, embodiment 2, embodiment 3, comparative example 1 is assembled into the electrochemical impedance spectrogram of lithium ion battery;
Fig. 3 is the preparation method of the silicon-carbon composite cathode pole piece using lithium ion battery provided by the invention, and the silicon-carbon composite cathode sheet made respectively in embodiment 1, embodiment 2, embodiment 3, comparative example 1 is assembled into the cycle performance figure of lithium ion battery.
Embodiment
In order to make those skilled in the art person understand the present invention program better, below in conjunction with drawings and embodiments, the present invention is described in further detail.
The invention provides a kind of silicon-carbon composite cathode pole piece of lithium ion battery, comprise negative current collector, the surface-coated of shown negative current collector has one deck silicon-carbon cathode active material layer.
In the present invention, in specific implementation, described negative current collector can be Copper Foil or the cated Copper Foil of surperficial tool, the thickness of described negative current collector is preferably 5 μm ~ 30 μm, wherein, the coating that described copper foil surface has can for the coating adopting at least one Material coating in graphite, Graphene, carbon nano-tube, agraphitic carbon, conductive black, acetylene black, conductive black SuperP to be formed.
In the present invention, in specific implementation, described silicon-carbon cathode active material layer comprise mass percent be 80% ~ 99.5% Si-C composite material, 0% ~ 15% graphene conductive agent, the carbon nanotube conducting agent of 0% ~ 15%, the carbon black conductive agent of 0% ~ 15% and 0.2% ~ 20% binding agent.
Wherein, in specific implementation, the silicon materials comprised in described Si-C composite material and the mass ratio of material with carbon element can be 1:(0.1 ~ 100).Wherein, described silicon materials can be nano-silicon, silica, the sub-silicon of oxidation or silicon-containing alloy; Described material with carbon element can be hard carbon, soft carbon, native graphite, Delanium or carbonaceous mesophase spherules.
Wherein, in specific implementation, described graphene conductive agent can comprise at least one in single-layer graphene, multi-layer graphene and modified graphene.
Wherein, in specific implementation, described carbon nanotube conducting agent can comprise at least one in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and modified carbon nano-tube.
Wherein, in specific implementation, described carbon black conductive agent can comprise at least one in graphite, agraphitic carbon, acetylene black and conductive black SuperP.
Wherein, in specific implementation, described binding agent can comprise at least one in carboxyl methyl cellulose, butadiene-styrene rubber, Kynoar, polytetrafluoroethylene, epoxy resin, polyvinyl alcohol, polyimides and polyacrylic acid.
Based on the silicon-carbon composite cathode pole piece of the lithium ion battery that the invention described above provides, present invention also offers a kind of lithium ion battery, it is non-aqueous secondary batteries, comprises anode pole piece, silicon-carbon composite cathode pole piece, barrier film and shell, is injected with nonaqueous electrolytic solution in the shell of described lithium ion battery.
In the present invention, the battery of the various shapes that described lithium ion battery can be well known to those skilled in the art can be such as the battery of the shape such as circular, square.
In addition, the preparation method of the silicon-carbon composite cathode pole piece of a kind of lithium ion battery that the present invention also provides, for the production of the silicon-carbon composite cathode pole piece that the invention described above provides, the method specifically comprises the following steps:
The first step, configuration carboxyl methyl cellulose glue: join in deionized water by carboxyl methyl cellulose powder, the solid content being formulated to glue is 0.1% ~ 10%, then stirs, and obtains CMC glue;
In a first step, be preferably: stir 4h ~ 24h with the mixing speed of 100rpm ~ 800rpm.
In a first step, in specific implementation, the condition that the ratio between described carboxyl methyl cellulose powder and deionized water should meet is: the mass ratio between described carboxyl methyl cellulose powder and deionized water is 1:(10 ~ 1000).
Second step, configuration conducting resinl: Graphene, carbon nano-tube and carbon black conductive agent are joined in described carboxyl methyl cellulose glue, then stirs and obtain conducting resinl;
In second step, be preferably: stir 0.5h ~ 2.5h with the mixing speed of 1500rpm ~ 4000rpm.
In second step, in specific implementation, the condition that described Graphene, carbon nano-tube, ratio between carbon black conductive agent and CMC glue should meet is: described Graphene, carbon nano-tube, mass ratio between carbon black conductive agent and CMC glue are: (0 ~ 15): (0 ~ 15): (0 ~ 15): 100.
3rd step, add silicon carbon material: in described conducting resinl, add material with carbon element and silicon materials simultaneously, after stirring, add solid content to 35% ~ 55% of deionized water adjustment conducting resinl, and then stir and mix, obtain the conducting resinl comprising silicon materials and material with carbon element;
In specific implementation, described 3rd step is specially: add material with carbon element and silicon materials in described conducting resinl after simultaneously, first stir 15min ~ 60min by the mixing speed of 100rpm ~ 800rpm, then 2h ~ 6h is stirred by the mixing speed of 1500rpm ~ 4000rpm, add solid content to 35% ~ 55% of deionized water adjustment conducting resinl, stir 0.5h ~ 1.5h by the mixing speed of 1500rpm ~ 4000rpm again, obtain the conducting resinl comprising silicon materials and material with carbon element.
In the third step, in specific implementation, the condition that described conducting resinl (not comprising conducting resinl when silicon materials and material with carbon element), material with carbon element, ratio between silicon materials and deionized water should meet is: described conducting resinl (not comprising conducting resinl when silicon materials and material with carbon element), material with carbon element, mass ratio between silicon materials and deionized water are (0.01 ~ 100): 1:(0.1 ~ 100): (0.1 ~ 100).
In the present invention, as previously mentioned, in the third step, in specific implementation, described silicon materials can be nano-silicon, silica, the sub-silicon of oxidation or silicon-containing alloy; Described material with carbon element can be hard carbon, soft carbon, native graphite, Delanium or carbonaceous mesophase spherules.
4th step, continues to add butadiene-styrene rubber: continue to add butadiene-styrene rubber to the 3rd comprising in the conducting resinl of silicon materials and material with carbon element of step acquisition, stir acquisition slurry;
In the 4th step, be preferably: stir 10 ~ 30min with the mixing speed of 100rpm ~ 800rpm.
In the 4th step, in specific implementation, described butadiene-styrene rubber and describedly comprise the condition that the ratio between silicon materials and the conducting resinl of material with carbon element should meet and be: described butadiene-styrene rubber and the described mass ratio comprised between silicon materials and the conducting resinl of material with carbon element are 1:(10 ~ 1000).
5th step, is sieved: filtered by 80 ~ 150 mesh sieves by described for acquisition slurry.
6th step, coating: the described slurry through filtering is coated on negative pole currect collecting surface, and carries out air blast by the blower fan be put in baking box simultaneously, realize heating, drying, the silicon-carbon composite cathode pole piece that the final the present invention of acquisition needs.
It should be noted that, in the 6th step, the coating speed of the described slurry through filtering can be 1m/min ~ 5m/min, the blast velocity of blower fan can be 500rpm ~ 1000rpm, oven temperature can be 50 DEG C ~ 130 DEG C, and the coating density of the active material layer (the described slurry namely after heating, drying) of negative pole currect collecting surface can be 10mg/cm 2~ 40mg/cm 2.
In the present invention, in specific implementation, in the 6th step, described negative current collector can be Copper Foil or the cated Copper Foil of surperficial tool, the thickness of described negative current collector is preferably 5 μm ~ 30 μm, wherein, the coating that described copper foil surface has can for the coating adopting at least one Material coating in graphite, Graphene, carbon nano-tube, agraphitic carbon, conductive black, acetylene black, conductive black SuperP to be formed.
Compared with prior art, the preparation method of the silicon-carbon composite cathode pole piece of a kind of lithium ion battery provided by the invention, has following advantage:
1, the preparation method of silicon-carbon composite cathode pole piece provided by the present invention is simple to operation, pollution-free, is applicable to suitability for industrialized production.
2, Graphene, carbon nano-tube, carbon black conductive agent are chosen suitable solvent (as CMC glue) dispersion by the present invention, thus make between silicon-carbon cathode particle, form a little-line-face multidimensional conductive network, for establishing good conductive channel between silicon-carbon cathode particle, the silicon-carbon composite cathode pole piece produced is made to have lower surface resistivity, and the Charge-transfer resistance of lithium ion battery can be reduced, improve the cyclical stability of lithium ion battery.
Below in conjunction with embodiment 1 to embodiment 3, the preparation method of the silicon-carbon composite cathode pole piece according to a kind of lithium ion battery provided by the invention is described, produces the detailed process of silicon-carbon composite cathode pole piece.
Embodiment 1
In specific embodiment 1, the present invention makes the lithium ion battery silicon-carbon composite negative pole pole piece of high conductivity, comprises the following steps:
The first step, configuration carboxyl methyl cellulose glue: join in deionized water by the CMC powder of 30g, the solid content being formulated to glue is 1.6%, with the speed low rate mixing 12h of 500rpm, stirs and obtains CMC glue;
Second step, configuration conducting resinl: the agent of 80g graphene conductive, the agent of 185g carbon nanotube conducting, 10gSuperP conductive agent are joined in described CMC glue, with the speed rapid stirring 1h of 3000rpm, obtains conducting resinl;
3rd step, add silicon carbon material: in the conducting resinl that described second step obtains, add the Delanium of 2.3kg and the sub-silicon of oxidation of 0.2kg simultaneously, after the speed low rate mixing 30min of 500rpm, the speed rapid stirring 4h of 2000rpm again, add the solid content to 45% of deionized water adjustment conducting resinl, and then with the speed rapid stirring 1h of 2000rpm;
4th step, adds butadiene-styrene rubber: continue to add 70g butadiene-styrene rubber binding agent to the 3rd comprising in the conducting resinl of silicon materials and material with carbon element of step acquisition, with the speed low rate mixing 20min of 100rpm, obtain slurry;
5th step, is sieved: filtered by 100 mesh sieves by the described slurry obtained;
6th step, coating: the Copper Foil negative pole currect collecting surface described slurry through filtering being coated on 8 μm of thickness, be coated with 2m/min coating speed, during coating, be put in baking box simultaneously and carry out air blast with blower fan, realize heating, drying, fan speed is 500rpm, oven temperature is 100 DEG C, and the coating density of the active material layer (the described slurry namely after heating, drying) of negative pole currect collecting surface is 20mg/cm 2.
For the present invention, in specific implementation, based on the silicon-carbon composite cathode pole piece that the invention described above prepares, the preparation method producing lithium ion battery is as follows:
The first step: rolled by the silicon-carbon composite cathode pole piece of the present embodiment 1 to thickness 110 μm, divides and is cut to the bar shaped pole piece that width is 74.5mm;
Second step: 3.5kg cobalt acid lithium, 28g polyvinylidene fluoride, the agent of 18g carbon nanotube conducting are mixed to join in N-methyl-2 pyrrolidones, adjustment solid content to 70%, first use the stirring at low speed 30min of 500rpm, then the high-speed stirred 4h of 2000rpm is used, obtain anode sizing agent, by 100 mesh screen.Anode sizing agent is coated on the aluminium foil anode collection surface of 12 μm of thickness, coating speed 3m/min, blower fan by placing in baking box during coating carries out blast heating oven dry, fan speed is 500rpm, oven temperature is 120 DEG C, and the coating density of the active material layer of anode collection surface is 44mg/cm 2.Pole piece is rolled to thickness 115 μm, divide and be cut to the bar shaped pole piece that width is 73mm, namely obtain anode pole piece;
3rd step: the cathode pole piece above-mentioned first step obtained, second step obtains anode pole piece and membrane coil winds, by plastic-aluminum shell encapsulation poling group, dry 12h under 90 degree of vacuum environments after, the nonaqueous electrolytic solution 7g of the lithium hexafluoro phosphate (i.e. solute) containing 1mol in solvent (ethylene carbonate, volume ratio between methyl ethyl carbonate and diethyl carbonate are 1:1:1) is injected in above-mentioned pole group, then seal, obtained lithium ion battery.Changed in the usual way subsequently by battery, the gas collection produced in formation process, in air bag, follow-uply to seal through vacuum suction.
4th step: be 3350mAh by obtained lithium ion battery design capacity, through to change into and after volume test, the thickness of lithium ion battery is 4mm, and average size is 3350mAh, namely finally obtains the lithium ion battery of embodiment 1.
Embodiment 2
In specific embodiment 2, the present invention makes the lithium ion battery silicon-carbon composite negative pole pole piece of high conductivity, comprises the following steps:
The first step, configuration carboxyl methyl cellulose glue: join in deionized water by the CMC powder of 30g, the solid content being formulated to glue is 1.2%, with the speed low rate mixing 12h of 400rpm, stirs and obtains CMC glue;
Second step, configuration conducting resinl: the agent of 160g graphene conductive, the agent of 100g carbon nanotube conducting, 10gSuperP conductive agent are joined in described CMC glue, with the speed rapid stirring 1h of 3000rpm, obtains conducting resinl;
3rd step, add silicon carbon material: in the conducting resinl that described second step obtains, add the Delanium of 2.3kg and the sub-silicon of oxidation of 0.2kg simultaneously, after the speed low rate mixing 30min of 600rpm, the speed rapid stirring 4h of 2000rpm again, add the solid content to 40% of deionized water adjustment conducting resinl, and then with the speed rapid stirring 1h of 2000rpm;
4th step, adds butadiene-styrene rubber: continue to add 70g butadiene-styrene rubber binding agent to the 3rd comprising in the conducting resinl of silicon materials and material with carbon element of step acquisition, with the speed low rate mixing 30min of 100rpm, obtain slurry;
5th step, is sieved: filtered by 100 mesh sieves by the described slurry obtained;
6th step, coating: the Copper Foil negative pole currect collecting surface described slurry through filtering being coated on 8 μm of thickness, be coated with 2m/min coating speed, during coating, be put in baking box simultaneously and carry out air blast with blower fan, realize heating, drying, fan speed is 500rpm, oven temperature is 100 DEG C, and the coating density of the active material layer (the described slurry namely after heating, drying) of negative pole currect collecting surface is 20mg/cm 2.
In example 2, its side of preparing lithium ion battery is identical with the method in embodiment 1, the final lithium ion battery obtaining embodiment 2.
Embodiment 3
In specific embodiment 3, the present invention makes the lithium ion battery silicon-carbon composite negative pole pole piece of high conductivity, comprises the following steps:
The first step, configuration carboxyl methyl cellulose glue: join in deionized water by the CMC powder of 30g, the solid content being formulated to glue is 5%, with the speed low rate mixing 24h of 300rpm, stirs and obtains CMC glue;
Second step, configuration conducting resinl: the agent of 40g graphene conductive, the agent of 160g carbon nanotube conducting, 20gSuperP conductive agent are joined in described CMC glue, with the speed rapid stirring 1h of 3000rpm, obtains conducting resinl;
3rd step, add silicon carbon material: in the conducting resinl that described second step obtains, add the Delanium of 2.3kg and the sub-silicon of oxidation of 0.2kg simultaneously, after the speed low rate mixing 30min of 300rpm, use the speed rapid stirring 6h of 2000rpm again, add the solid content to 50% of deionized water adjustment conducting resinl, and then with the speed rapid stirring 0.5h of 2000rpm;
4th step, adds butadiene-styrene rubber: continue to add 70g butadiene-styrene rubber binding agent to the 3rd comprising in the conducting resinl of silicon materials and material with carbon element of step acquisition, with the speed low rate mixing 15min of 100rpm, obtain slurry;
5th step, is sieved: filtered by 100 mesh sieves by the described slurry obtained;
6th step, coating: the Copper Foil negative pole currect collecting surface described slurry through filtering being coated on 8 μm of thickness, be coated with the coating speed of 2m/min, during coating, be put in baking box simultaneously and carry out air blast with blower fan, realize heating, drying, fan speed is 500rpm, oven temperature is 100 DEG C, and the coating density of the active material layer (the described slurry namely after heating, drying) of negative pole currect collecting surface is 20mg/cm 2.
In embodiment 3, its side of preparing lithium ion battery is identical with the method in embodiment 1, the final lithium ion battery obtaining embodiment 3.
Comparative example 1
In comparative example 1, the manufacture method of a kind of silicon-carbon composite cathode pole piece adopted is identical with embodiment 1, and unique difference is when configuring conducting resinl in second step, only adds the SuperP conductive agent of 275g.
In comparative example 1, its side of preparing lithium ion battery is identical with the method in embodiment 1, the final lithium ion battery obtaining comparative example 1.
In the present invention, by silicon-carbon composite cathode pole piece obtained for embodiment 1, embodiment 2, embodiment 3 and comparative example 1, utilize four point probe resistivity tester to test the surface resistivity of cathode pole piece.
Test result is as shown in table 1 below:
Surface resistivity (milliohm/square)
Embodiment 1 85
Embodiment 2 102
Embodiment 3 117
Comparative example 1 189
As can be seen from the result of upper table 1, the surface resistivity of embodiment 1, embodiment 2, embodiment 3 is starkly lower than the surface resistivity of comparative example 1, has more excellent electronic conduction.
Fig. 1 is the preparation method using silicon-carbon composite cathode pole piece provided by the invention, at the Electronic Speculum figure of the silicon-carbon composite cathode pole piece that embodiment 1 is made, Fig. 2 is the preparation method using silicon-carbon composite cathode pole piece provided by the invention, in embodiment 1, embodiment 2, embodiment 3, the silicon-carbon composite cathode sheet that comparative example 1 is made respectively is assembled into the electrochemical impedance spectrogram of lithium ion battery, Fig. 3 is the preparation method using silicon-carbon composite cathode pole piece provided by the invention, in embodiment 1, embodiment 2, embodiment 3, the silicon-carbon composite cathode sheet that comparative example 1 is made respectively is assembled into the cycle performance figure of lithium ion battery.
As shown in Figure 1, the graphene conductive agent in the silicon-carbon composite cathode pole piece that embodiment 1 is obtained, carbon nanotube conducting agent, SuperP conductive agent are evenly distributed in the surface of silicon-carbon cathode material.By the lithium ion battery that embodiment 1, embodiment 2, embodiment 3, comparative example 1 obtain, test electrochemical impedance spectroscopy (EIS) by electrochemical workstation, by the cycle performance of Arbin lithium ion battery testing equipment test battery." be that the coordinate of general received EIS collection of illustrative plates illustrates, Z' is the real part of EIS, Z " is the imaginary part of EIS in Fig. 2, Z' and-Z.As shown in Figure 2, the electric transmission impedance of the lithium ion battery of embodiment 1, embodiment 2, embodiment 3 is starkly lower than comparative example 1, is conducive to the transmission of electronics.
As shown in Figure 3, when charge and discharge cycles 450 times, embodiment 1, embodiment 2, embodiment 3 capacity of lithium ion battery conservation rate apparently higher than comparative example 1.
Fig. 1, Fig. 2 and Fig. 3 fully indicate the silicon-carbon composite cathode pole piece prepared with the present invention, can ensure to apply its lithium ion battery prepared further and have that electric transmission impedance is low, cyclical stability high.
Therefore, known based on statement above, compared with prior art, silicon-carbon composite cathode pole piece of a kind of lithium ion battery provided by the invention and preparation method thereof, this silicon-carbon composite cathode pole piece effectively can improve the electric conductivity of silica-base material, ensure that the lithium ion battery impedance that cathode pole piece is applied is low, have extended cycle life, increase substantially the overall performance of lithium ion battery, the long user demand of electronic product can be met, be conducive to the market application foreground improving cell production companies product, be of great practical significance.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (10)

1. a silicon-carbon composite cathode pole piece for lithium ion battery, is characterized in that, comprise negative current collector, and the surface-coated of shown negative current collector has one deck silicon-carbon cathode active material layer;
Described silicon-carbon cathode active material layer comprise mass percent be 80% ~ 99.5% Si-C composite material, 0% ~ 15% graphene conductive agent, the carbon nanotube conducting agent of 0% ~ 15%, the carbon black conductive agent of 0% ~ 15% and 0.2% ~ 20% binding agent.
2. silicon-carbon composite cathode pole piece as claimed in claim 1, it is characterized in that, described negative current collector is Copper Foil or the cated Copper Foil of surperficial tool;
The coating that described copper foil surface has is the coating adopting at least one Material coating in graphite, Graphene, carbon nano-tube, agraphitic carbon, conductive black, acetylene black, conductive black SuperP to be formed.
3. silicon-carbon composite cathode pole piece as claimed in claim 1, it is characterized in that, the silicon materials comprised in described Si-C composite material and the mass ratio of material with carbon element are 1:(0.1 ~ 100);
Described silicon materials are nano-silicon, silica, the sub-silicon of oxidation or silicon-containing alloy; Described material with carbon element is hard carbon, soft carbon, native graphite, Delanium or carbonaceous mesophase spherules.
4. silicon-carbon composite cathode pole piece as claimed in claim 1, it is characterized in that, described graphene conductive agent comprises at least one in single-layer graphene, multi-layer graphene and modified graphene;
Described carbon nanotube conducting agent comprises at least one in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and modified carbon nano-tube;
Described carbon black conductive agent comprises at least one in graphite, agraphitic carbon, acetylene black and conductive black SuperP;
Described binding agent comprises at least one in carboxyl methyl cellulose, butadiene-styrene rubber, Kynoar, polytetrafluoroethylene, epoxy resin, polyvinyl alcohol, polyimides and polyacrylic acid.
5. a preparation method for the silicon-carbon composite cathode pole piece of lithium ion battery, is characterized in that, comprise the following steps:
The first step, joins in deionized water by carboxyl methyl cellulose powder, and the solid content being formulated to glue is 0.1% ~ 10%, then stirs, and obtains CMC glue;
Second step, joins Graphene, carbon nano-tube and carbon black conductive agent in described carboxyl methyl cellulose glue, then stirs and obtain conducting resinl;
3rd step, adds material with carbon element and silicon materials in described conducting resinl simultaneously, after stirring, adds solid content to 35% ~ 55% of deionized water adjustment conducting resinl, and then stirs and mix, obtain the conducting resinl comprising silicon materials and material with carbon element;
4th step, continued to add butadiene-styrene rubber to described comprising in the conducting resinl of silicon materials and material with carbon element, and stir acquisition slurry;
5th step, filters described for acquisition slurry;
6th step, is coated on negative pole currect collecting surface by the described slurry through filtering, and carries out air blast by the blower fan be put in baking box simultaneously, realize heating, drying, final acquisition silicon-carbon composite cathode pole piece.
6. preparation method as claimed in claim 5, it is characterized in that, in a first step, the mass ratio between described carboxyl methyl cellulose powder and deionized water is 1:(10 ~ 1000);
In second step, described Graphene, carbon nano-tube, mass ratio between carbon black conductive agent and CMC glue are: (0 ~ 15): (0 ~ 15): (0 ~ 15): 100;
In the 4th step, described butadiene-styrene rubber and the described mass ratio comprised between silicon materials and the conducting resinl of material with carbon element are 1:(10 ~ 1000).
7. preparation method as claimed in claim 5, is characterized in that, in a first step, stirs 4h ~ 24h with the mixing speed of 100rpm ~ 800rpm;
In second step, stir 0.5h ~ 2.5h with the mixing speed of 1500rpm ~ 4000rpm;
In the 4th step, stir 10min ~ 30min with the mixing speed of 100rpm ~ 800rpm.
8. preparation method as claimed in claim 5, it is characterized in that, described 3rd step is specially: add material with carbon element and silicon materials in described conducting resinl after simultaneously, first stir 15min ~ 60min by the mixing speed of 100rpm ~ 800rpm, then 2h ~ 6h is stirred by the mixing speed of 1500rpm ~ 4000rpm, add solid content to 35% ~ 55% of deionized water adjustment conducting resinl, stir 0.5h ~ 1.5h by the mixing speed of 1500rpm ~ 4000rpm again, obtain the conducting resinl comprising silicon materials and material with carbon element.
9. the preparation method as described in claim 5 or 7, it is characterized in that, in the third step, described conducting resinl, material with carbon element, mass ratio between silicon materials and deionized water are (0.01 ~ 100): 1:(0.1 ~ 100): (0.1 ~ 100);
Wherein said silicon materials are nano-silicon, silica, the sub-silicon of oxidation or silicon-containing alloy, and described material with carbon element is hard carbon, soft carbon, native graphite, Delanium or carbonaceous mesophase spherules.
10. preparation method as claimed in claim 5, it is characterized in that, described 5th step is specially: filtered by 80 ~ 150 mesh sieves by described for acquisition slurry.
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Application publication date: 20160511