CN103811719B - A kind of lithium ion battery silicon negative electrode and preparation method thereof and lithium ion battery - Google Patents

A kind of lithium ion battery silicon negative electrode and preparation method thereof and lithium ion battery Download PDF

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CN103811719B
CN103811719B CN201210445842.9A CN201210445842A CN103811719B CN 103811719 B CN103811719 B CN 103811719B CN 201210445842 A CN201210445842 A CN 201210445842A CN 103811719 B CN103811719 B CN 103811719B
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ion battery
lithium ion
negative electrode
silicium cathode
silicon
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CN103811719A (en
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张麒
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Huawei Technologies Co Ltd
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Huawei Technologies Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0464—Electro organic synthesis
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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

Embodiments provide a kind of lithium ion battery silicon negative electrode, including collector and coating silicium cathode active material layer on a current collector, the material of silicium cathode active material layer includes silicon materials, binding agent, conductive agent and pore creating material, pore creating material is ethylene carbonate or the polymer of its homologue formation of grafting electron withdraw group, and pore creating material accounts for the 5% ~ 25% of silicium cathode active material gross weight.Pore creating material can be reduced decomposition under electronegative potential and generate gas and lithium carbonate, pore-creating on silicium cathode pole piece after gas effusion, form the lithium ion battery silicon negative electrode with loose structure, the existence of loose structure can be the expansion headspace that silicon materials occur in charge and discharge process, therefore, it is possible to ensure to have between preferable connectivity and silicon materials and conductive agent between silicon materials have good connectivity.The embodiment of the present invention additionally provides the preparation method of a kind of lithium ion battery silicon negative electrode and comprises the lithium ion battery of this lithium ion battery silicon negative electrode.

Description

A kind of lithium ion battery silicon negative electrode and preparation method thereof and lithium ion battery
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of lithium ion battery silicon negative electrode and Preparation method and lithium ion battery.
Background technology
In numerous energy storage technologies, lithium ion battery due to have lightweight, volume is little, running voltage is high, Energy density is high, output is big, charge efficiency is high, memory-less effect, the advantage such as have extended cycle life, The field such as mobile phone, notebook computer is widely used.
But the electronic digital product such as smart mobile phone and the panel computer energy density requirement to lithium ion battery at present More and more higher, and the negative material graphite of commercialization is difficult to meet energy density requirement.The theory gram of silicon materials is held Amount is 4200mAh/g, and far above the theoretical gram volume 372mAh/g of graphite material, but silicon materials are in discharge and recharge During volumetric expansion big, make silicon materials be difficult to commercialization at present in flexible-packed battery, be in particular in: (1) silicon materials volumetric expansion causes cathode pole piece thickness to increase, and then causes lithium ion battery volume to increase； (2) silicon materials volumetric expansion causes the reduction that contacts between silicon materials and between silicon materials with conductive carbon, sternly Ghost image rings the service life cycle of lithium ion battery；(3) easily come off from collector after silicon materials volumetric expansion, Easily cause the safety problem such as self discharge and internal short-circuit.
For enable silicon materials commercialization in the cathode pole piece of lithium ion battery, the currently research weight to silicon materials Point for how controlling silicon materials expands.Using more way at present is to be optimized silicon materials with modified, Such as using nano silica fume, silicon nanowires, nano-tube or silicon-carbon compound, also someone uses vapour deposition process Amorphous carbon deposits nano-silicon, although the circulation that these methods improve silicium cathode to a certain extent is steady Qualitative, but the effect that these methods improve stability is limited, and prepare the complex process of these silicon materials, Process energy consumption is big, adds the cost of lithium ion battery, it is difficult to realize the commercialization produced in enormous quantities.
Additionally, also it has been proposed that prepare the electrode of porous silicon-based cathode.Such as, Publication No. CN101894940A Chinese patent application file by silicon-based anode slurry add pore former (ammonium fluoride, ammonium chloride, nitre Acid ammonium etc.), carry out high temperature drying the most under a shielding gas, make pore former evaporate, i.e. prepare negative pole During at negative pole headspace, obtain the silicon-based anode containing porous.But this preparation method needs in protection Carrying out under high temperature in gas, energy consumption is big, and process costs is high, and pore former used has corrosivity, meeting Corrosion copper current collector, containing certain toxicity, is difficult to safety in production.The most such as, Publication No. The Chinese patent application file of CN101192663A adds during preparing electrode in electrode slurry to be made Pore polymer (zinc-containing solid catalyst, polyalkylene oxides, polyalkylsiloxane, polyacrylic acid alkyl The polymer such as ester, polyalkyl methacrylate or copolymer), when this electrode is used for preparing battery, pore-creating Polymer is infiltrated in electrolyte solution, during now pore creating material is dissolved in electrolyte thus in active material layer Play the effect forming hole.Although this preparation method is easily operated, but the pore-creating polymer wherein used and electricity The bulk composition solving liquid is different, electrolyte component will be caused to change, affect lithium the most at last after being dissolved in electrolyte The performance of ion battery.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of lithium ion battery silicon negative electrode, in order to Solve the lithium ion that in prior art, the volumetric expansion in charge and discharge process of lithium ion battery negative silicon materials brings Battery volume increases, lithium ion battery service life cycle shortens, self discharge and internal short-circuit easily occur and existing Have during pore creating material is easily soluble in electrolyte present in lithium ion battery negative in technology and cause electrolyte component to be sent out The raw problem changed.Embodiment of the present invention second aspect provides the preparation of this lithium ion battery silicon negative electrode Method, in order to solve, existing porous silicon cathode pole piece energy consumption is big, process costs is high, be difficult to safety in production Problem.The embodiment of the present invention third aspect provide the lithium comprising described lithium ion battery silicon negative electrode from Sub-battery, this lithium ion battery energy density is high and has extended cycle life.
First aspect, embodiments provides a kind of lithium ion battery silicon negative electrode, including collector and The silicium cathode active material layer being coated on described collector, the material of described silicium cathode active material layer includes Silicon materials, binding agent, conductive agent and pore creating material, described pore creating material is the ethylene carbonate of grafting electron withdraw group The polymer that ester or its homologue are formed, described pore creating material accounts for the 5% ~ 25% of silicium cathode active material gross weight.
Preferably, the polymerization of one or more during described pore creating material is the polymer at least containing below general formula I Composition granule,
Formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO2, CN or halogen, n is 10 ~ 10000 Integer.
Preferably, described pore creating material has the weight average molecular weight of 500 ~ 1000000.
Preferably, described pore creating material accounts for the 10% ~ 20% of silicium cathode active material gross weight.
Preferably, described silicon materials are nano silicon particles, aluminosilicate alloy material, silica carbon composite or nano-silicon / silica composite.
Preferably, described binding agent is Kynoar, politef, epoxy resin, polyvinyl alcohol, gathers One or more in acid imide and polyurethane.
Preferably, described conductive agent be graphite, expanded graphite, CNT, carbon fiber, activated carbon, without fixed One or more in shape carbon, conductive black, acetylene black, Super P and KS-6.
Preferably, described silicon materials, binding agent and conductive agent account for silicium cathode active material gross weight respectively 60% ~ 90%, 4% ~ 10% and 1% ~ 5%.
Preferably, the thickness of described silicium cathode active material layer is 30 ~ 200 μm.
Preferably, described collector is plane Copper Foil or foam Copper Foil.
In a kind of lithium ion battery silicon negative electrode that embodiment of the present invention first aspect provides, pore creating material is grafting The polymer that the ethylene carbonate of electron withdraw group or its homologue are formed, described pore creating material can under electronegative potential Be reduced decomposition and generate gas and lithium carbonate, after gas effusion can pore-creating on silicium cathode pole piece, thus formed Having the lithium ion battery silicon negative electrode of loose structure, the existence of loose structure can be that silicon materials are in charge and discharge The expansion headspace occurred in electric process, therefore, it is possible to ensure to have between silicon materials preferable connectivity with And there is between silicon materials and conductive agent good connectivity, thus improve the energy density of lithium ion battery, Promote the cycle life of lithium ion battery.
Second aspect, embodiments provides the preparation method of a kind of lithium ion battery silicon negative electrode, bag Include following steps:
(1) silicon materials, binding agent, conductive agent and pore creating material composition silicium cathode slurry solids dispensing component are taken, Described solid ingredient component is disperseed in organic solvent, stirring, prepare silicium cathode slurry, described pore creating material The polymer formed for ethylene carbonate or its homologue of grafting electron withdraw group, described pore creating material accounts for described The 5% ~ 25% of silicium cathode slurry solids dispensing component weight；
(2) described silicium cathode slurry is coated on collection liquid surface, is dried and roll-in, prepare lithium ion Battery silicium cathode pole piece.
Preferably, the polymerization of one or more during described pore creating material is the polymer at least containing below general formula I Composition granule,
Formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO2, CN or halogen, n is 10 ~ 10000 Integer.
Preferably, described pore creating material has the weight average molecular weight of 500 ~ 1000000.
Preferably, described pore creating material accounts for the 10% ~ 20% of described silicium cathode slurry solids dispensing component weight.
Preferably, silicon materials are nano silicon particles, aluminosilicate alloy material, silica carbon composite or nano-silicon/bis- Silica composite.
Preferably, described binding agent is Kynoar, politef, epoxy resin, polyvinyl alcohol, gathers One or more in acid imide and polyurethane.
Preferably, conductive agent be graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, One or more in conductive black, acetylene black, Super P and KS-6.
Preferably, described silicon materials, binding agent and conductive agent account for silicium cathode slurry solids dispensing component gross weight respectively 60% ~ 90%, 4% ~ 10% and the 1% ~ 5% of amount.
Preferably, organic solvent be DMF (DMF), N,N-dimethylacetamide (DMAc), One or more in N-2-methyl pyrrolidone (NMP), oxolane (THF), acetone and methanol.
Preferably, in described silicium cathode slurry, percetage by weight shared by organic solvent is 30% ~ 70%.
Described silicium cathode slurry includes silicium cathode slurry solids dispensing and organic solvent.Described silicium cathode slurry is at warp Crossing and be dried and after roll-in, silicium cathode slurry solids dispensing therein coating forms silicium cathode activity on a current collector Material layer.
Preferably, described collector is plane Copper Foil or foam Copper Foil.
Preferably, whipping temp is 0 ~ 50 DEG C, and mixing time is 2 ~ 12 hours.
The preparation method of a kind of lithium ion battery silicon negative electrode that embodiment of the present invention second aspect provides, the party Method does not change the production procedure of traditional lithium-ion battery silicium cathode pole piece, simple, with low cost, without dirty Dye, it is easy to industrialized production.
The third aspect, embodiments provides lithium ion battery, and described lithium ion battery is implemented by the present invention Lithium ion battery silicon negative electrode that example first aspect provides, anode pole piece, barrier film, nonaqueous electrolytic solution and outer Shell forms, and described shell is can open formation or have the housing of air bag.
Preferably, described shell is aluminum plastic film housing, square box hat or aluminum hull housing.
Preferably, containing positive electrode active materials on anode pole piece, described positive electrode active materials selected from LiFePO4, Lithium manganese phosphate, phosphoric acid vanadium lithium, ferric metasilicate lithium, cobalt acid lithium, nickel-cobalt-manganese ternary material, nickel manganese/cobalt manganese/nickel cobalt two One or more in raw material, LiMn2O4, lithium-rich nickel ion doped.
Preferably, described barrier film is polyethylene polymer, polyacrylic polymer or non-woven fabrics.
Lithium ion battery silicon negative electrode, including collector and the silicium cathode activity material being coated on described collector The bed of material, the material of described silicium cathode active material layer includes silicon materials, binding agent, conductive agent and pore creating material, The polymer that described pore creating material is the grafting ethylene carbonate of electron withdraw group or its homologue is formed, described in make Hole agent accounts for the 5% ~ 25% of silicium cathode slurry solids component weight.
Described lithium ion battery is after chemical conversion, and the pore creating material in lithium ion battery silicon negative electrode is under electronegative potential Decomposition can be reduced and generate gas and lithium carbonate, after gas effusion can pore-creating on silicium cathode pole piece, form tool Having the lithium ion battery silicon negative electrode of loose structure, the existence of loose structure can be that silicon materials are in discharge and recharge During the expansion headspace that occurs, therefore, it is possible to ensure to have between silicon materials preferable connectivity and There is between silicon materials and conductive agent good connectivity, thus improve the energy density of lithium ion battery, carry Rise the cycle life of lithium ion battery.Meanwhile, the lithium carbonate of production is deposited on silicium cathode active material layer surface Form SEI film.
The lithium ion battery energy density that the embodiment of the present invention third aspect provides is high and has extended cycle life.
The advantage of the embodiment of the present invention will partly illustrate, and a part according to description is It will be apparent that or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of lithium ion battery silicon negative electrode in the specific embodiment of the invention.
Detailed description of the invention
The following stated is the preferred implementation of the embodiment of the present invention, it is noted that general for the art For logical technical staff, on the premise of without departing from embodiment of the present invention principle, it is also possible to make some improvement And retouching, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of lithium ion battery silicon negative electrode, in order to solve existing skill The lithium ion battery volume that in art, the volumetric expansion in charge and discharge process of lithium ion battery negative silicon materials brings increases Greatly, lithium ion battery service life cycle shortens, lithium in self discharge and internal short-circuit and prior art easily occurs Present in ion battery negative pole, pore creating material is easily soluble in electrolyte and causes what electrolyte component changed to ask Topic.Embodiment of the present invention second aspect provides the preparation method of this lithium ion battery silicon negative electrode, in order to Solve the problem that existing porous silicon cathode pole piece energy consumption is big, process costs is high, be difficult to safety in production.This The inventive embodiments third aspect provides the lithium ion battery comprising described lithium ion battery silicon negative electrode, should Lithium ion battery energy density is high and has extended cycle life.
First aspect, embodiments provides a kind of lithium ion battery silicon negative electrode, including collector and The silicium cathode active material layer being coated on described collector, the material of described silicium cathode active material layer includes Silicon materials, binding agent, conductive agent and pore creating material, described pore creating material is the ethylene carbonate of grafting electron withdraw group The polymer that ester or its homologue are formed, described pore creating material accounts for the 5% ~ 25% of silicium cathode active material gross weight.
Described pore creating material is the polymer beads of one or more in the polymer at least containing below general formula I,
Formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO2, CN or halogen, n is 10 ~ 10000 Integer.
Described pore creating material has the weight average molecular weight of 500 ~ 1000000.
Described pore creating material accounts for the 10% ~ 20% of silicium cathode active material gross weight.
Described silicon materials are nano silicon particles, aluminosilicate alloy material, silica carbon composite or nano-silicon/titanium dioxide Silicon compound.
Described binding agent be Kynoar, politef, epoxy resin, polyvinyl alcohol, polyimides and One or more in polyurethane.
Described conductive agent is graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, leads One or more in electricity white carbon black, acetylene black, Super P and KS-6.
Described silicon materials, binding agent and conductive agent account for respectively silicium cathode active material gross weight 60% ~ 90%, 4% ~ 10% and 1% ~ 5%.
The thickness of described silicium cathode active material layer is 30 ~ 200 μm.
Described collector is plane Copper Foil or foam Copper Foil.
In a kind of lithium ion battery silicon negative electrode that embodiment of the present invention first aspect provides, pore creating material is grafting The polymer that the ethylene carbonate of electron withdraw group or its homologue are formed, described pore creating material can under electronegative potential Be reduced decomposition and generate gas and lithium carbonate, after gas effusion can pore-creating on silicium cathode pole piece, thus formed Having the lithium ion battery silicon negative electrode of loose structure, the existence of loose structure can be that silicon materials are in charge and discharge The expansion headspace occurred in electric process, therefore, it is possible to ensure to have between silicon materials preferable connectivity with And there is between silicon materials and conductive agent good connectivity, thus improve the energy density of lithium ion battery, Promote the cycle life of lithium ion battery.
Second aspect, embodiments provides the preparation method of a kind of lithium ion battery silicon negative electrode, bag Include following steps:
(1) silicon materials, binding agent, conductive agent and pore creating material composition silicium cathode slurry solids dispensing component are taken, Described solid ingredient component is disperseed in organic solvent, stirring, prepare silicium cathode slurry, described pore creating material The polymer formed for ethylene carbonate or its homologue of grafting electron withdraw group, described pore creating material accounts for described The 5% ~ 25% of silicium cathode slurry solids dispensing component weight；
(2) described silicium cathode slurry is coated on collection liquid surface, is dried and roll-in, prepare lithium ion Battery silicium cathode pole piece.
Described pore creating material is the polymer beads of one or more in the polymer at least containing below general formula I,
Formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO2, CN or halogen, n is 10 ~ 10000 Integer.
Described pore creating material has the weight average molecular weight of 500 ~ 1000000.
Described pore creating material accounts for the 10% ~ 20% of described silicium cathode slurry solids dispensing component weight.
Silicon materials are that nano silicon particles, aluminosilicate alloy material, silica carbon composite or nanometer silicon/silicon dioxide are multiple Compound.
Described binding agent be Kynoar, politef, epoxy resin, polyvinyl alcohol, polyimides and One or more in polyurethane.
Conductive agent is graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conduction charcoal One or more in black, acetylene black, Super P and KS-6.
Described silicon materials, binding agent and conductive agent account for silicium cathode slurry solids dispensing component weight respectively 60% ~ 90%, 4% ~ 10% and 1% ~ 5%.
Organic solvent is N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), N-2-first One or more in base ketopyrrolidine (NMP), oxolane (THF), acetone and methanol.
In described silicium cathode slurry, the percetage by weight shared by organic solvent is 30% ~ 70%.
Described silicium cathode slurry includes silicium cathode slurry solids dispensing and organic solvent.Described silicium cathode slurry is at warp Crossing and be dried and after roll-in, silicium cathode slurry solids dispensing therein coating forms silicium cathode activity on a current collector Material layer.
Described collector is plane Copper Foil or foam Copper Foil.
Whipping temp is 0 ~ 50 DEG C, and mixing time is 2 ~ 12 hours.
The preparation method of a kind of lithium ion battery silicon negative electrode that embodiment of the present invention second aspect provides, the party Method does not change the production procedure of traditional lithium-ion battery silicium cathode pole piece, simple, with low cost, without dirty Dye, it is easy to industrialized production.
The third aspect, embodiments provides lithium ion battery, and described lithium ion battery is implemented by the present invention Lithium ion battery silicon negative electrode that example first aspect provides, anode pole piece, barrier film, nonaqueous electrolytic solution and outer Shell forms, and described shell is can open formation or have the housing of air bag.
Described shell is aluminum plastic film housing, square box hat or aluminum hull housing.
Anode pole piece is made up of collector and coating positive electrode active materials on a current collector.Described positive-active material Material selected from LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium, ferric metasilicate lithium, cobalt acid lithium, nickel-cobalt-manganese ternary material, One or more in nickel manganese/cobalt manganese/nickel cobalt two raw material, LiMn2O4, lithium-rich nickel ion doped.
Described barrier film is polyethylene polymer, polyacrylic polymer or non-woven fabrics.
Nonaqueous electrolytic solution is the electrolyte of carbonate solvent, and containing lithium salts in described electrolyte, described carbonic ester selects From ethylene carbonate (EC), Allyl carbonate (PC), dimethyl carbonate (DMC) and Ethyl methyl carbonate (EMC) one or more in, described lithium salts is selected from LiPF6、LiBF4、LiSbF6、LiClO4、LiCF3SO3、 LiAlO4、LiAlCl4, Li(CF3SO2)2One or more in N, LiBOB and LiDFOB.
Lithium ion battery silicon negative electrode, including collector and the silicium cathode activity material being coated on described collector The bed of material, the material of described silicium cathode active material layer includes silicon materials, binding agent, conductive agent and pore creating material, The polymer that described pore creating material is the grafting ethylene carbonate of electron withdraw group or its homologue is formed, described in make Hole agent accounts for the 5% ~ 25% of silicium cathode active material gross weight.
The making of lithium ion battery
By the lithium ion battery silicon negative electrode in embodiment of the present invention according to battery capacity specification and battery core Production method divides and is cut into sheet strip, directly and anode slice of lithium ion battery is wound or lamination molding, Add microporous separators between both positive and negative polarity, be assembled fluid injection, sealing after encapsulation, all by industry technical staff The technique being familiar with is carried out, without particular determination.
The lithium ion battery prepared subsequently enters chemical conversion step.Described lithium ion battery through chemical conversion after, lithium from Pore creating material in sub-battery silicium cathode pole piece can be reduced decomposition under electronegative potential and generate gas and lithium carbonate, gas After body effusion can pore-creating on silicium cathode pole piece, formed and there is the lithium ion battery silicon negative electrode of loose structure, The existence of loose structure can be the expansion headspace that silicon materials occur in charge and discharge process, therefore, it is possible to Ensure to have between preferable connectivity and silicon materials and conductive agent between silicon materials that there is good connection Property, thus improve the energy density of lithium ion battery, promote the cycle life of lithium ion battery.Meanwhile, raw The lithium carbonate produced is deposited on silicium cathode active material layer surface and forms SEI film.
In lithium ion battery after chemical conversion, the voidage of silicium cathode active material layer is 10% ~ 50%, pore size It it is 0.01 ~ 10 μm.
The lithium ion battery energy density that the embodiment of the present invention third aspect provides is high and has extended cycle life.
The embodiment of the present invention is not limited to following specific embodiment.In the range of constant principal right, permissible Suitable carrying out change is implemented.
Embodiment one
The preparation method of a kind of lithium ion battery silicon negative electrode, comprises the following steps:
(1) nano-silicon/silica composite, Kynoar, acetylene black and poly-4-cyano group carbonic acid are taken respectively Vinyl acetateAs silicium cathode slurry solids dispensing component, by 25 Gram Kynoar, joins in the N-2-methylpyrrolidone solution of 500 grams, stirs 4 hours, then Adding 50 grammes per square metre average molecular weights is 25000, and dispersion index PDI is the poly-4-cyano group ethylene carbonate of 1.6, Stirring at low speed 2 hours, is subsequently added 25 grams of acetylene blacks, stirring at low speed 2 hours, be eventually adding nano-silicon/ Silica composite 400 grams, stirring at low speed 2 hours, whipping temp is 25 DEG C, then cold at 8 DEG C But high speed dispersion 1 hour under the protection of water, obtains stable silicium cathode slurry；
(2) described silicium cathode slurry being coated on plane copper foil surface, coat weight is 5.26g/cm2(do not contain Copper Foil), it is placed in the baking oven of 80 DEG C and is dried, then carrying out roll-in to pole piece thickness is 0.078mm, point It is cut to the stripe shape pole piece that width is 40mm, prepares lithium ion battery silicon negative electrode.
The lithium ion battery silicon negative electrode that the present embodiment prepares includes collector and is coated on described collector Silicium cathode active material layer, the material of silicium cathode active material layer includes silicon materials, binding agent, conductive agent And pore creating material, pore creating material is poly-4-cyano group ethylene carbonate, and described pore creating material accounts for silicium cathode active material gross weight The 10% of amount.
The preparation method of lithium ion battery
The lithium ion battery silicon negative electrode that the present embodiment prepares is cut into certain length.
By 200 grams of positive electrode active materials LiCoO2, 6 grams of binding agent polyvinylidene fluoride (PVDF), 4 grams lead The mixture of electricity agent acetylene black joins in 60 grams of N-methyl-2 pyrrolidone solution (NMP), and first low speed stirs Mixing 4 hours, then under the protection of 8 DEG C of cooling water, high speed dispersion forms uniform anode sizing agent in 1 hour.Will This anode sizing agent is coated on the aluminium foil of 16 microns uniformly, and the surface density controlling coating is 23g/cm2, so Dry at latter 120 DEG C, through being rolled into required thickness, then cut into the positive pole pole that width is 39mm Sheet, and cut into the anode pole piece mating above-mentioned cathode pole piece length demand.
Handy to cathode pole piece obtained above, anode pole piece and membrane winding aluminum plastic film is sealed in advance, will be at solvent (carbon Acid ethyl: methyl ethyl carbonate: diethyl carbonate volume ratio is 1:1:1) in containing 1 mole six The nonaqueous electrolytic solution of lithium fluophosphate 10 grams injects in the above-mentioned naked battery core sealed the most completely, then seals.
The lithium ion battery prepared is melted into the most in a conventional manner, and the collection and confinement of gases produced in formation process is at gas In capsule, follow-up through bleeding sealing.
The design capacity of this lithium ion battery is 2000 MAHs, after chemical conversion and volume test, and lithium ion The thickness of battery is 5.5mm, and average size is 2000 MAHs.
Embodiment two
Present embodiment is unlike embodiment one, and described silicium cathode formula of size is: nano-silicon/titanium dioxide Silicon compound is 325g, and Kynoar is 20g, and acetylene black is 30g, and poly-4-cyano group ethylene carbonate is 125g.Other preparation methods of lithium ion battery are identical with embodiment one.
The lithium ion battery that embodiment two prepares, its negative pole thickness is 0.078mm, and average initial capacity is 2000mAh。
Embodiment three
Present embodiment is unlike embodiment one and embodiment two, and described silicium cathode formula of size is: nanometer Silicon/silicon dioxide complex is 420g, and Kynoar is 25g, and acetylene black is 30g, poly-4-cyano group carbonic acid Vinyl acetate is 25g.Other preparation methods of lithium ion battery are identical with embodiment one and embodiment two.
Embodiment two prepares lithium ion battery, and its negative pole thickness is 0.078mm, and average initial capacity is 2000mAh。
Comparative example one
The preparation method of comparative example one is identical with embodiment one, two and embodiment three, only in the system of silicium cathode slurry Pore creating material it is added without during Bei.The cathode pole piece thickness that comparative example one prepares also is 0.078mm, Soft Roll electricity Pond original depth is also configured as 5.5mm, and average size is 2000mAh.
By in embodiment one, embodiment two and embodiment three and comparative example one through chemical conversion product respectively through Gather one-shot battery capacity data after 20 circulations, 100 circulations, and disassemble percentage of batteries, measure negative pole The average thickness of pole piece, result is as shown in table 1.
Table 1. embodiment one, embodiment two and embodiment three compare with comparative example one properties of product
Embodiment four
The preparation method of a kind of lithium ion battery silicon negative electrode, comprises the following steps:
(1) silicon-carbon alloy material, polytetrafluoroethylene (PTFE), Super P and poly-(carbonic acid 2-are taken respectively Nitro propylene)As silicium cathode slurry solids dispensing component, by 25 grams poly-four Fluorothene (PTFE), joins in the DMF solution of 500 grams, stirs 4 hours, connects Addition 100 grammes per square metre average molecular weights is 50000, and dispersion index PDI is poly-(the carbonic acid 2-nitro third of 1.7 Alkene ester), stirring at low speed 2 hours, it is subsequently added 25 grams of Super P, stirring at low speed 2 hours, is eventually adding Silicon-carbon alloy material 350 grams, stirring at low speed 2 hours, whipping temp is 30 DEG C, then 8 DEG C of coolings High speed dispersion 1 hour under the protection of water, obtains stable silicium cathode slurry；
(2) described silicium cathode slurry being coated on plane copper foil surface, coat weight is 5.26g/cm2(do not contain Copper Foil), it is placed in the baking oven of 80 DEG C and is dried, then carrying out roll-in to pole piece thickness is 0.079mm, point It is cut to the stripe shape pole piece that width is 46mm, prepares lithium ion battery silicon negative electrode.
The lithium ion battery silicon negative electrode that the present embodiment prepares includes collector and is coated on described collector Silicium cathode active material layer, the material of silicium cathode active material layer includes silicon materials, binding agent, conductive agent And pore creating material, pore creating material is poly-(carbonic acid 2-nitro propylene), and it is total that described pore creating material accounts for silicium cathode active material The 20% of weight.
The preparation method of lithium ion battery
The lithium ion battery silicon negative electrode that the present embodiment prepares is cut into certain length.
By 200 grams of positive electrode active materials LiCoO2, 5 grams of binding agent polyvinylidene fluoride (PVDF), 6 grams lead The mixture of electricity agent acetylene black joins in 300 grams of N-methyl-2 pyrrolidone solution (NMP), and first low speed stirs Mixing 4 hours, then under the protection of 8 DEG C of cooling water, high speed dispersion forms uniform anode sizing agent in 1 hour.Will This anode sizing agent is coated on the aluminium foil of 16 microns uniformly, and the surface density controlling coating is 21g/cm2, so Dry at latter 130 DEG C, through being rolled into required thickness, then cut into the positive pole pole that width is 44mm Sheet, and cut into the anode pole piece mating above-mentioned cathode pole piece length demand.
Cathode pole piece obtained above, anode pole piece and membrane coil are wound sheath body and enters 103450 type standard square Aluminum hull housing, will solvent (ethylene carbonate: methyl ethyl carbonate: diethyl carbonate volume ratio is 1:1: 1) nonaqueous electrolytic solution 10 grams of the lithium hexafluoro phosphate containing 1 mole in injects in above-mentioned aluminum hull liquid injection hole.
The lithium ion battery open formation the most in a conventional manner prepared, in high temperature formation process, gas never seals The liquid injection hole effusion of mouth, seals by steel ball.
This lithium ion battery design thickness is 9.8mm, and battery core design rolling thickness is 9.0mm, design capacity For 1800mAh, after volume test, first charge-discharge average size is 1800mAh, lithium ion battery Sample average thickness is 10.0mm.
Comparative example two
The preparation method of comparative example two is identical with embodiment four, is only added without in the preparation process of silicium cathode slurry Pore creating material.The cathode pole piece thickness that comparative example two prepares also is 0.079mm, and rectangular cell original depth also sets Being calculated as 9.8mm, battery core design rolling thickness is 9.0mm, and recording average size is 1800mAh, averagely thick Degree is 10.0mm.
Embodiment four is passed through the product of chemical conversion respectively through 20 circulations, 100 circulations in comparative example two Rear collection one-shot battery capacity data, and disassemble percentage of batteries, measure the average thickness of cathode pole piece, result As shown in table 2.
Table 2. embodiment four compares with comparative example two properties of product
Embodiment five
The preparation method of a kind of lithium ion battery silicon negative electrode, comprises the following steps:
(1) silica carbon composite, Kynoar, acetylene black and poly-(carbonic acid 2-fluorothene ester) are taken respectivelyAs silicium cathode slurry solids dispensing component, by 25 grams of poly-inclined fluorine Ethylene, joins in the N-2-methylpyrrolidone solution of 500 grams, stirs 4 hours, is subsequently added into 50 grams Weight average molecular weight is 5000, and purity profile PDI is poly-(the carbonic acid 2-fluorothene ester) of 1.3, stirring at low speed 2 Hour, it is subsequently added 25 grams of acetylene blacks, stirring at low speed 2 hours, is eventually adding silica carbon composite 400 Gram, stirring at low speed 2 hours, whipping temp is 25 DEG C, then divides at a high speed under the protection of 8 DEG C of cooling water Dissipate 1 hour, obtain stable silicium cathode slurry；
(2) described silicium cathode slurry being coated on plane copper foil surface, coat weight is 5.26g/cm2(do not contain Copper Foil), it is placed in the baking oven of 80 DEG C and is dried, then carrying out roll-in to pole piece thickness is 0.079mm, point It is cut to the stripe shape pole piece that width is 46mm, prepares lithium ion battery silicon negative electrode.
The lithium ion battery silicon negative electrode that the present embodiment prepares includes collector and is coated on described collector Silicium cathode active material layer, the material of silicium cathode active material layer includes silicon materials, binding agent, conductive agent And pore creating material, pore creating material is poly-(carbonic acid 2-fluoropropene ester), and described pore creating material accounts for silicium cathode active material gross weight The 20% of amount.
To sum up, the lithium ion battery that the embodiment of the present invention third aspect provides energy density after chemical conversion high and Having extended cycle life, in the case of other material is identical, energy conservation rate can promote 10～25%, circulates the longevity Life can promote 20 ~ 50%.

Claims (10)

1. a lithium ion battery silicon negative electrode, it is characterised in that include collector and be coated in described collection Silicium cathode active material layer on fluid, the material of described silicium cathode active material layer includes silicon materials, bonding Agent, conductive agent and pore creating material, described pore creating material is ethylene carbonate or its homologue of grafting electron withdraw group The polymer formed, described pore creating material accounts for the 5%～25% of silicium cathode active material gross weight.
2. lithium ion battery silicon negative electrode as claimed in claim 1 a kind of, it is characterised in that described in make Hole agent is the polymer beads of one or more in the polymer at least containing below general formula I,
Formula I:
Wherein, R is the chain-like alkyl of H or C1～C6, and R ' is NO2, CN or halogen, n is 10～10000 Integer.
3. lithium ion battery silicon negative electrode as claimed in claim 1 a kind of, it is characterised in that described in make Hole agent has the weight average molecular weight of 500～1000000.
4. a kind of lithium ion battery silicon negative electrode as claimed in claim 1, it is characterised in that described silicon Material is nano silicon particles, aluminosilicate alloy material, silica carbon composite or nano-silicon/silica composite.
5. a kind of lithium ion battery silicon negative electrode as claimed in claim 1, it is characterised in that described silicon Material, binding agent and conductive agent account for 60%～90%, 4%～10% and of silicium cathode active material gross weight respectively 1%～5%.
6. a kind of lithium ion battery silicon negative electrode as claimed in claim 1, it is characterised in that described silicon The thickness of anode active material layer is 30～200 μm.
7. the preparation method of a lithium ion battery silicon negative electrode, it is characterised in that comprise the following steps:
(1) silicon materials, binding agent, conductive agent and pore creating material composition silicium cathode slurry solids dispensing component are taken, Described solid ingredient component is disperseed in organic solvent, stirring, prepare silicium cathode slurry, described pore creating material The polymer formed for ethylene carbonate or its homologue of grafting electron withdraw group, described pore creating material accounts for described The 5%～25% of silicium cathode slurry solids dispensing component weight；
(2) described silicium cathode slurry is coated on collection liquid surface, is dried and roll-in, prepare lithium ion Battery silicium cathode pole piece.
The preparation method of a kind of lithium ion battery silicon negative electrode the most as claimed in claim 7, its feature exists In, described pore creating material is the polymer beads of one or more in the polymer at least containing below general formula I, Formula I:
Wherein, R is the chain-like alkyl of H or C1～C6, and R ' is NO2, CN or halogen, n is 10～10000 Integer.
The preparation method of a kind of lithium ion battery silicon negative electrode the most as claimed in claim 7, its feature exists In, described pore creating material has the weight average molecular weight of 500～1000000.
10. a lithium ion battery, it is characterised in that described lithium ion battery is by as appointed in claim 1～6 Lithium ion battery silicon negative electrode described in one claim, anode pole piece, barrier film, nonaqueous electrolytic solution and outer Shell forms, and described shell is can open formation or have the housing of air bag.
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