CN103811719A - Lithium ion battery silicon negative electrode plate and its preparation method and lithium ion battery - Google Patents
Lithium ion battery silicon negative electrode plate and its preparation method and lithium ion battery Download PDFInfo
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- CN103811719A CN103811719A CN201210445842.9A CN201210445842A CN103811719A CN 103811719 A CN103811719 A CN 103811719A CN 201210445842 A CN201210445842 A CN 201210445842A CN 103811719 A CN103811719 A CN 103811719A
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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
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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
- H01M4/13—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
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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
- 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
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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
- H01M4/13—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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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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
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
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- 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
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- 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 embodiment of the invention provides a lithium ion battery silicon negative electrode plate including a current collector and a silicon negative electrode active material layer coating the current collector, the silicon negative electrode active material layer comprises materials of a silicon material, a binder, a conductive agent and a pore forming agent, the pore forming agent is a polymer formed by electron-withdrawing-group grafted ethylene carbonate or a homologous compound thereof, and the pore forming agent accounts for 5% to 25% of the total weight of the silicon negative electrode active material layer. The pore forming agent at low potentials can be decomposed by reduction into gases and lithium carbonate, the gases escape to form pores on a silicon negative electrode plate and further form the lithium ion battery silicon negative electrode plate with a porous structure, and the porous structure exists for reservation of space for expansion of the silicon material in the process of charge and discharge, so that a better connectivity between the silicon material and a good connectivity between the silicon material and the conductive agent can be ensured. The embodiment of the invention also provides a preparation method of the lithium ion battery silicon negative electrode plate and a lithium ion battery comprising the lithium ion battery silicon negative electrode plate.
Description
Technical field
The present invention relates to lithium ion battery field, particularly relate to a kind of lithium ion battery silicon cathode pole piece and preparation method thereof and lithium ion battery.
Background technology
In numerous energy storage technologies, lithium ion battery is lightweight owing to having, volume is little, operating voltage is high, energy density is high, power output is large, charge efficiency is high, memory-less effect, the advantage such as have extended cycle life, and is widely used in the field such as mobile phone, notebook computer.
But it is more and more higher that the electronic digital products such as current smart mobile phone and panel computer require the energy density of lithium ion battery, and commercial negative material graphite is difficult to meet energy density requirement.The theoretical gram volume of silicon materials is 4200mAh/g, far above the theoretical gram volume 372mAh/g of graphite material, but silicon materials volumetric expansion in charge and discharge process is large, make silicon materials in flexible-packed battery, be difficult at present commercialization, be in particular in: (1) silicon materials volumetric expansion causes cathode pole piece thickness to increase, and then cause that lithium ion battery volume increases; (2) silicon materials volumetric expansion cause between silicon materials and silicon materials and conductive carbon between contact reduction, have a strong impact on the service life cycle of lithium ion battery; (3) after silicon materials volumetric expansion, easily come off from collector, easily cause the safety problem such as self discharge and internal short-circuit.
For make silicon materials can commercialization in the cathode pole piece of lithium ion battery, current the research emphasis of silicon materials for how controlling silicon materials is expanded.Adopting more way is at present that silicon materials are optimized and modification, such as adopting nano silica fume, silicon nanowires, nano-tube or silicon-carbon are compound, also someone adopts vapour deposition process depositing nano silicon on amorphous carbon, although these methods have improved the cyclical stability of silicium cathode to a certain extent, it is limited that but these methods improve the effect of stability, and prepare the complex process of these silicon materials, process energy consumption is large, increase the cost of lithium ion battery, be difficult to realize the commercialization of producing in enormous quantities.
In addition, also someone proposes to prepare the electrode of porous silicon-based cathode.For example; publication number is that the Chinese patent application file of CN101894940A by adding pore former (ammonium fluoride, ammonium chloride, ammonium nitrate etc.) in silicon-based anode slurry; then under protective gas, carry out hyperthermia drying; make pore former evaporation; in the process of preparing negative pole at negative pole headspace, obtain the silicon-based anode that contains porous.But this preparation method need to carry out under high temperature in protective gas, and energy consumption is large, and process costs is high, and pore former used has corrosivity, can corrode copper current collector, contains certain toxicity, is difficult for safety in production.Again for example, publication number is that the Chinese patent application file of CN101192663A adds pore-creating polymer polymer or copolymers such as () zinc-containing solid catalyst, polyalkylene oxides, poly-alkylsiloxane, polyalkyl acrylate, polyalkyl methacrylates in the process of preparing electrode in electrode slurry, this electrode is during for the preparation of battery, pore-creating polymer is infiltrated in electrolyte solution, thereby now pore creating material is dissolved in the effect of playing formation hole in electrolyte in active material layer.Although this preparation method's easy operating, the pore-creating polymer wherein using is different from the main body composition of electrolyte, is dissolved in after electrolyte and will causes electrolyte component variation, affects the most at last the performance of lithium 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 cathode pole piece, shortens, is prone to the soluble problem that causes electrolyte component to change of the pore creating material existing in lithium ion battery negative in self discharge and internal short-circuit and prior art in order to solve the increase of the lithium ion battery negative silicon materials lithium ion battery volume that volumetric expansion brings in charge and discharge process, lithium ion battery service life cycle in prior art in electrolyte.Embodiment of the present invention second aspect provides the preparation method of this lithium ion battery silicon cathode pole piece, and in order to solve, existing porous silicon cathode pole piece energy consumption is large, process costs is high, the problem of difficult safety in production.The embodiment of the present invention third aspect provides the lithium ion battery that comprises described lithium ion battery silicon cathode pole piece, and this lithium ion battery energy density is high and have extended cycle life.
First aspect, the embodiment of the present invention provides a kind of lithium ion battery silicon cathode pole piece, comprise collector and be coated in the silicium cathode active material layer on described collector, the material of described silicium cathode active material layer comprises silicon materials, binding agent, conductive agent and pore creating material, described pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, and described pore creating material accounts for 5% ~ 25% of silicium cathode active material total weight.
Preferably, described pore creating material is one or more the polymer beads at least containing in the polymer of following general formula I,
General formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO
2, CN or halogen, the integer that n is 10 ~ 10000.
Preferably, described pore creating material has 500 ~ 1000000 weight average molecular weight.
Preferably, described pore creating material accounts for 10% ~ 20% of silicium cathode active material total 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 one or more in Kynoar, polytetrafluoroethylene, epoxy resin, polyvinyl alcohol, polyimides and polyurethane.
Preferably, described conductive agent is one or more in graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, acetylene black, Super P and KS-6.
Preferably, described silicon materials, binding agent and conductive agent account for respectively 60% ~ 90%, 4% ~ 10% and 1% ~ 5% of silicium cathode active material total weight.
Preferably, the thickness of described silicium cathode active material layer is 30 ~ 200 μ m.
Preferably, described collector is plane Copper Foil or foam Copper Foil.
In a kind of lithium ion battery silicon cathode pole piece that embodiment of the present invention first aspect provides, pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, described pore creating material can be reduced to decompose and generate gas and lithium carbonate under electronegative potential, gas can pore-creating on silicium cathode pole piece after overflowing, thereby form the lithium ion battery silicon cathode pole piece with loose structure, the expansion headspace that the existence of loose structure can occur for silicon materials in charge and discharge process, therefore can guarantee to have between good connectivity and silicon materials and conductive agent and there is good connectivity between silicon materials, thereby improve the energy density of lithium ion battery, promote the cycle life of lithium ion battery.
Second aspect, the embodiment of the present invention provides a kind of preparation method of lithium ion battery silicon cathode pole piece, comprises the following steps:
(1) get silicon materials, binding agent, conductive agent and pore creating material composition silicium cathode slurry solids furnish component, described solid ingredient component is disperseed in organic solvent, stir, make silicium cathode slurry, described pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, and described pore creating material accounts for 5% ~ 25% of described silicium cathode slurry solids furnish component total weight;
(2) described silicium cathode slurry is coated on to collection liquid surface, is dried and roll-in, make lithium ion battery silicon cathode pole piece.
Preferably, described pore creating material is one or more the polymer beads at least containing in the polymer of following general formula I,
General formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO
2, CN or halogen, the integer that n is 10 ~ 10000.
Preferably, described pore creating material has 500 ~ 1000000 weight average molecular weight.
Preferably, described pore creating material accounts for 10% ~ 20% of described silicium cathode slurry solids furnish component total weight.
Preferably, silicon materials are nano silicon particles, aluminosilicate alloy material, silica carbon composite or nano-silicon/silica composite.
Preferably, described binding agent is one or more in Kynoar, polytetrafluoroethylene, epoxy resin, polyvinyl alcohol, polyimides and polyurethane.
Preferably, conductive agent is one or more in graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, acetylene black, Super P and KS-6.
Preferably, described silicon materials, binding agent and conductive agent account for respectively 60% ~ 90%, 4% ~ 10% and 1% ~ 5% of silicium cathode slurry solids furnish component total weight.
Preferably, organic solvent is N, one or more in dinethylformamide (DMF), DMA (DMAc), N-2-methyl pyrrolidone (NMP), oxolane (THF), acetone and methyl alcohol.
Preferably, in described silicium cathode slurry, the shared percetage by weight of organic solvent is 30% ~ 70%.
Described silicium cathode slurry comprises silicium cathode slurry solids batching and organic solvent.Described silicium cathode slurry is after super-dry and roll-in, and silicium cathode slurry solids batching is wherein coated in and on collector, forms silicium cathode active material layer.
Preferably, described collector is plane Copper Foil or foam Copper Foil.
Preferably, whipping temp is 0 ~ 50 ℃, and mixing time is 2 ~ 12 hours.
The preparation method of a kind of lithium ion battery silicon cathode pole piece that embodiment of the present invention second aspect provides, the method does not change the production procedure of conventional lithium ion battery silicon cathode pole piece, simple, with low cost, pollution-free, is easy to suitability for industrialized production.
The third aspect, the embodiment of the present invention provides lithium ion battery, lithium ion battery silicon cathode pole piece, anode pole piece, barrier film, nonaqueous electrolytic solution and shell that described lithium ion battery is provided by embodiment of the present invention first aspect form, and described shell is can open formation or have a housing of air bag.
Preferably, described shell is aluminum plastic film housing, square box hat or aluminum hull housing.
Preferably, on anode pole piece, contain positive electrode active materials, described positive electrode active materials is selected from one or more in 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 raw material, LiMn2O4, rich lithium stratiform nickel LiMn2O4.
Preferably, described barrier film is polyethylene polymer, polyacrylic polymer or nonwoven fabrics.
Lithium ion battery silicon cathode pole piece, comprise collector and be coated in the silicium cathode active material layer on described collector, the material of described silicium cathode active material layer comprises silicon materials, binding agent, conductive agent and pore creating material, described pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, and described pore creating material accounts for 5% ~ 25% of silicium cathode slurry solids component total weight.
Described lithium ion battery is after changing into, pore creating material in lithium ion battery silicon cathode pole piece can be reduced to decompose and generate gas and lithium carbonate under electronegative potential, gas can pore-creating on silicium cathode pole piece after overflowing, formation has the lithium ion battery silicon cathode pole piece of loose structure, the expansion headspace that the existence of loose structure can occur for silicon materials in charge and discharge process, therefore can guarantee to have between good connectivity and silicon materials and conductive agent and there is good connectivity between silicon materials, thereby improve the energy density of lithium ion battery, promote the cycle life of lithium ion battery.Meanwhile, the lithium carbonate of production is deposited on silicium cathode active material layer surface and forms SEI film.
Lithium ion battery energy density that the embodiment of the present invention third aspect provides is high and have extended cycle life.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can know 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 cathode pole piece in the specific embodiment of the invention.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of lithium ion battery silicon cathode pole piece, shortens, is prone to the soluble problem that causes electrolyte component to change of the pore creating material existing in lithium ion battery negative in self discharge and internal short-circuit and prior art in order to solve the increase of the lithium ion battery negative silicon materials lithium ion battery volume that volumetric expansion brings in charge and discharge process, lithium ion battery service life cycle in prior art in electrolyte.Embodiment of the present invention second aspect provides the preparation method of this lithium ion battery silicon cathode pole piece, and in order to solve, existing porous silicon cathode pole piece energy consumption is large, process costs is high, the problem of difficult safety in production.The embodiment of the present invention third aspect provides the lithium ion battery that comprises described lithium ion battery silicon cathode pole piece, and this lithium ion battery energy density is high and have extended cycle life.
First aspect, the embodiment of the present invention provides a kind of lithium ion battery silicon cathode pole piece, comprise collector and be coated in the silicium cathode active material layer on described collector, the material of described silicium cathode active material layer comprises silicon materials, binding agent, conductive agent and pore creating material, described pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, and described pore creating material accounts for 5% ~ 25% of silicium cathode active material total weight.
Described pore creating material is one or more the polymer beads at least containing in the polymer of following general formula I,
General formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO
2, CN or halogen, the integer that n is 10 ~ 10000.
Described pore creating material has 500 ~ 1000000 weight average molecular weight.
Described pore creating material accounts for 10% ~ 20% of silicium cathode active material total weight.
Described silicon materials are nano silicon particles, aluminosilicate alloy material, silica carbon composite or nano-silicon/silica composite.
Described binding agent is one or more in Kynoar, polytetrafluoroethylene, epoxy resin, polyvinyl alcohol, polyimides and polyurethane.
Described conductive agent is one or more in graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, acetylene black, Super P and KS-6.
Described silicon materials, binding agent and conductive agent account for respectively 60% ~ 90%, 4% ~ 10% and 1% ~ 5% of silicium cathode active material total weight.
The thickness of described silicium cathode active material layer is 30 ~ 200 μ m.
Described collector is plane Copper Foil or foam Copper Foil.
In a kind of lithium ion battery silicon cathode pole piece that embodiment of the present invention first aspect provides, pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, described pore creating material can be reduced to decompose and generate gas and lithium carbonate under electronegative potential, gas can pore-creating on silicium cathode pole piece after overflowing, thereby form the lithium ion battery silicon cathode pole piece with loose structure, the expansion headspace that the existence of loose structure can occur for silicon materials in charge and discharge process, therefore can guarantee to have between good connectivity and silicon materials and conductive agent and there is good connectivity between silicon materials, thereby improve the energy density of lithium ion battery, promote the cycle life of lithium ion battery.
Second aspect, the embodiment of the present invention provides a kind of preparation method of lithium ion battery silicon cathode pole piece, comprises the following steps:
(1) get silicon materials, binding agent, conductive agent and pore creating material composition silicium cathode slurry solids furnish component, described solid ingredient component is disperseed in organic solvent, stir, make silicium cathode slurry, described pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, and described pore creating material accounts for 5% ~ 25% of described silicium cathode slurry solids furnish component total weight;
(2) described silicium cathode slurry is coated on to collection liquid surface, is dried and roll-in, make lithium ion battery silicon cathode pole piece.
Described pore creating material is one or more the polymer beads at least containing in the polymer of following general formula I,
General formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO
2, CN or halogen, the integer that n is 10 ~ 10000.
Described pore creating material has 500 ~ 1000000 weight average molecular weight.
Described pore creating material accounts for 10% ~ 20% of described silicium cathode slurry solids furnish component total weight.
Silicon materials are nano silicon particles, aluminosilicate alloy material, silica carbon composite or nano-silicon/silica composite.
Described binding agent is one or more in Kynoar, polytetrafluoroethylene, epoxy resin, polyvinyl alcohol, polyimides and polyurethane.
Conductive agent is one or more in graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, acetylene black, Super P and KS-6.
Described silicon materials, binding agent and conductive agent account for respectively 60% ~ 90%, 4% ~ 10% and 1% ~ 5% of silicium cathode slurry solids furnish component total weight.
Organic solvent is one or more in DMF (DMF), DMA (DMAc), N-2-methyl pyrrolidone (NMP), oxolane (THF), acetone and methyl alcohol.
In described silicium cathode slurry, the shared percetage by weight of organic solvent is 30% ~ 70%.
Described silicium cathode slurry comprises silicium cathode slurry solids batching and organic solvent.Described silicium cathode slurry is after super-dry and roll-in, and silicium cathode slurry solids batching is wherein coated in and on collector, forms silicium cathode active material layer.
Described collector is plane Copper Foil or foam Copper Foil.
Whipping temp is 0 ~ 50 ℃, and mixing time is 2 ~ 12 hours.
The preparation method of a kind of lithium ion battery silicon cathode pole piece that embodiment of the present invention second aspect provides, the method does not change the production procedure of conventional lithium ion battery silicon cathode pole piece, simple, with low cost, pollution-free, is easy to suitability for industrialized production.
The third aspect, the embodiment of the present invention provides lithium ion battery, lithium ion battery silicon cathode pole piece, anode pole piece, barrier film, nonaqueous electrolytic solution and shell that described lithium ion battery is provided by embodiment of the present invention first aspect form, and described shell is can open formation or have a 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 the positive electrode active materials being coated on collector.Described positive electrode active materials is selected from one or more in 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 raw material, LiMn2O4, rich lithium stratiform nickel LiMn2O4.
Described barrier film is polyethylene polymer, polyacrylic polymer or nonwoven fabrics.
Nonaqueous electrolytic solution is the electrolyte of carbonate solvent, in described electrolyte, contain lithium salts, described carbonic ester is selected from one or more in ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), and described lithium salts is selected from LiPF
6, LiBF
4, LiSbF
6, LiClO
4, LiCF
3sO
3, LiAlO
4, LiAlCl
4, Li(CF
3sO
2)
2one or more in N, LiBOB and LiDFOB.
Lithium ion battery silicon cathode pole piece, comprise collector and be coated in the silicium cathode active material layer on described collector, the material of described silicium cathode active material layer comprises silicon materials, binding agent, conductive agent and pore creating material, described pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, and described pore creating material accounts for 5% ~ 25% of silicium cathode active material total weight.
The making of lithium ion battery
Lithium ion battery silicon cathode pole piece in embodiment of the present invention is divided and is cut into sheet strip according to the production method of battery capacity specification and battery core, directly and anode slice of lithium ion battery is reeled or lamination moulding, between both positive and negative polarity, add micropore barrier film, fluid injection after assembled package, sealing, all undertaken by the familiar technique of industry technical staff, without particular determination.
The lithium ion battery making enters subsequently and changes into step.Described lithium ion battery is after changing into, pore creating material in lithium ion battery silicon cathode pole piece can be reduced to decompose and generate gas and lithium carbonate under electronegative potential, gas can pore-creating on silicium cathode pole piece after overflowing, formation has the lithium ion battery silicon cathode pole piece of loose structure, the expansion headspace that the existence of loose structure can occur for silicon materials in charge and discharge process, therefore can guarantee to have between good connectivity and silicon materials and conductive agent and there is good connectivity between silicon materials, thereby improve the energy density of lithium ion battery, promote the cycle life of lithium ion battery.Meanwhile, the lithium carbonate of production is deposited on silicium cathode active material layer surface and forms SEI film.
In lithium ion battery after changing into, the voidage of silicium cathode active material layer is 10% ~ 50%, and pore size is 0.01 ~ 10 μ m.
Lithium ion battery energy density that the embodiment of the present invention third aspect provides is high and have extended cycle life.
The embodiment of the present invention is not limited to following specific embodiment.In the scope of constant principal right, carrying out that can be suitable changed and implements.
Embodiment mono-
A preparation method for lithium ion battery silicon cathode pole piece, comprises the following steps:
(1) get respectively nano-silicon/silica composite, Kynoar, acetylene black and poly-4-cyano group ethylene carbonate
as silicium cathode slurry solids furnish component, by 25 grams of Kynoar, join in the N-2-methyl pyrrolidone solution of 500 grams, stir 4 hours, then adding 50 grammes per square metre average molecular weights is 25000, dispersion index PDI is 1.6 poly-4-cyano group ethylene carbonate, stirring at low speed 2 hours, add subsequently 25 grams of acetylene blacks, stirring at low speed 2 hours, finally adds 400 grams of nano-silicon/silica composites, stirring at low speed 2 hours, whipping temp is 25 ℃, and then high speed dispersion 1 hour under the protection of 8 ℃ of cooling waters, obtains stable silicium cathode slurry;
(2) described silicium cathode slurry is coated on to plane copper foil surface, coat weight is 5.26g/cm
2(not containing Copper Foil), the baking oven that is placed in 80 ℃ is dried, and then carrying out roll-in to pole piece thickness is 0.078mm, divides and is cut to the stripe shape pole piece that width is 40mm, makes lithium ion battery silicon cathode pole piece.
The lithium ion battery silicon cathode pole piece that the present embodiment makes comprises collector and is coated in the silicium cathode active material layer on described collector, the material of silicium cathode active material layer comprises 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 10% of silicium cathode active material total weight.
The preparation method of lithium ion battery
The lithium ion battery silicon cathode pole piece that the present embodiment is made cuts into certain length.
By 200 grams of positive electrode active materials LiCoO
2, 6 grams of binding agent polyvinylidene fluoride (PVDF), 4 grams of conductive agent acetylene blacks mixture join in 60 grams of N-methyl-2 pyrrolidone solution (NMP); first stirring at low speed 4 hours, then under the protection of 8 ℃ of cooling waters, high speed dispersion forms uniform anode sizing agent for 1 hour.This anode sizing agent is coated on uniformly on the aluminium foil of 16 microns, the surface density of controlling coating is 23g/cm
2, then dry at 120 ℃, through being rolled into needed thickness, then cut into the anode pole piece that width is 39mm, and cut into the anode pole piece of the above-mentioned cathode pole piece length demand of coupling.
Handy to cathode pole piece obtained above, anode pole piece and membrane winding aluminum plastic film is sealed in advance, the above-mentioned not naked battery core of complete involution of 10 grams of injections of nonaqueous electrolytic solution of the lithium hexafluoro phosphate that will contain 1 mole in solvent (ethylene carbonate: Methylethyl carbonic ester: diethyl carbonate volume ratio is 1:1:1), then seals.
The lithium ion battery making changes into subsequently in a conventional manner, the gas collection producing in formation process in air bag, the sealing of bleeding of follow-up process.
The design capacity of this lithium ion battery is 2000 MAHs, through changing into and volume test after, the thickness of lithium ion battery is 5.5mm, average size is 2000 MAHs.
Embodiment bis-
Present embodiment is different from embodiment mono-, and described silicium cathode formula of size is: nano-silicon/silica composite 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 mono-.
The lithium ion battery that embodiment bis-makes, its negative pole thickness is 0.078mm, average initial capacity is 2000mAh.
Embodiment tri-
Present embodiment is different with embodiment bis-from embodiment mono-, and described silicium cathode formula of size is: nano-silicon/silica composite is 420g, and Kynoar is 25g, and acetylene black is 30g, and poly-4-cyano group ethylene carbonate is 25g.Other preparation methods of lithium ion battery are identical with embodiment mono-and embodiment bis-.
Embodiment bis-makes 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 tri-with embodiment mono-, two, only in the preparation process of silicium cathode slurry, does not add pore creating material.The cathode pole piece thickness that comparative example one makes is also 0.078mm, and soft-package battery original depth is also designed to 5.5mm, and average size is 2000mAh.
To in embodiment mono-, embodiment bis-and embodiment tri-and comparative example one, gather primary cell capacity data respectively through the product changing into after 20 circulations, 100 circulations, and disassemble part battery, measure the average thickness of cathode pole piece, result is as shown in table 1.
Table 1. embodiment mono-, embodiment bis-and embodiment tri-and comparative example one properties of product comparison
Embodiment tetra-
A preparation method for lithium ion battery silicon cathode pole piece, comprises the following steps:
(1) get respectively silicon-carbon alloy material, polytetrafluoroethylene (PTFE), Super P and gather (carbonic acid 2-nitro propylene)
as silicium cathode slurry solids furnish component, by 25 grams of polytetrafluoroethylene (PTFE)s, join the N of 500 grams, in dinethylformamide solution, stir 4 hours, then adding 100 grammes per square metre average molecular weights is 50000, dispersion index PDI is 1.7 poly-(carbonic acid 2-nitro propylene), and stirring at low speed 2 hours, adds 25 grams of Super P subsequently, stirring at low speed 2 hours, finally add 350 grams of silicon-carbon alloy materials, stirring at low speed 2 hours, whipping temp is 30 ℃, then high speed dispersion 1 hour under the protection of 8 ℃ of cooling waters, obtains stable silicium cathode slurry;
(2) described silicium cathode slurry is coated on to plane copper foil surface, coat weight is 5.26g/cm
2(not containing Copper Foil), the baking oven that is placed in 80 ℃ is dried, and then carrying out roll-in to pole piece thickness is 0.079mm, divides and is cut to the stripe shape pole piece that width is 46mm, makes lithium ion battery silicon cathode pole piece.
The lithium ion battery silicon cathode pole piece that the present embodiment makes comprises collector and is coated in the silicium cathode active material layer on described collector, the material of silicium cathode active material layer comprises silicon materials, binding agent, conductive agent and pore creating material, pore creating material is poly-(carbonic acid 2-nitro propylene), and described pore creating material accounts for 20% of silicium cathode active material total weight.
The preparation method of lithium ion battery
The lithium ion battery silicon cathode pole piece that the present embodiment is made cuts into certain length.
By 200 grams of positive electrode active materials LiCoO
2, 5 grams of binding agent polyvinylidene fluoride (PVDF), 6 grams of conductive agent acetylene blacks mixture join in 300 grams of N-methyl-2 pyrrolidone solution (NMP); first stirring at low speed 4 hours, then under the protection of 8 ℃ of cooling waters, high speed dispersion forms uniform anode sizing agent for 1 hour.This anode sizing agent is coated on uniformly on the aluminium foil of 16 microns, the surface density of controlling coating is 21g/cm
2, then dry at 130 ℃, through being rolled into needed thickness, then cut into the anode pole piece that width is 44mm, and cut into the anode pole piece of the above-mentioned cathode pole piece length demand of coupling.
Cathode pole piece obtained above, anode pole piece and membrane coil are wound to sheath body and enter the square aluminum hull housing of 103450 type standard, 10 grams of above-mentioned aluminum hull liquid injection holes of injection of nonaqueous electrolytic solution of the lithium hexafluoro phosphate that will contain 1 mole in solvent (ethylene carbonate: Methylethyl carbonic ester: diethyl carbonate volume ratio is 1:1:1).
The lithium ion battery making open formation in a conventional manner subsequently, in high temperature formation process, gas is overflowed from unsealed liquid injection hole, seals by steel ball.
This lithium ion battery design thickness is 9.8mm, and battery core design coiling thickness is 9.0mm, and design capacity is 1800mAh, and after volume test, first charge-discharge average size is 1800mAh, and lithium ion battery sample average thickness is 10.0mm.
Comparative example two
The preparation method of comparative example two is identical with embodiment tetra-, only in the preparation process of silicium cathode slurry, does not add pore creating material.The cathode pole piece thickness that comparative example two makes is also 0.079mm, and rectangular cell original depth is also designed to 9.8mm, and battery core design coiling thickness is 9.0mm, and recording average size is 1800mAh, and average thickness is 10.0mm.
To in embodiment tetra-and comparative example two, gather primary cell capacity data respectively through the product changing into after 20 circulations, 100 circulations, and disassemble part battery, measure the average thickness of cathode pole piece, result is as shown in table 2.
Table 2. embodiment tetra-and comparative example two properties of product comparisons
Embodiment five
A preparation method for lithium ion battery silicon cathode pole piece, comprises the following steps:
(1) get respectively silica carbon composite, Kynoar, acetylene black and gather (carbonic acid 2-PVF ester)
as silicium cathode slurry solids furnish component, by 25 grams of Kynoar, join in the N-2-methyl pyrrolidone solution of 500 grams, stir 4 hours, then adding 50 grammes per square metre average molecular weights is 5000, purity profile PDI is 1.3 poly-(carbonic acid 2-PVF ester), stirring at low speed 2 hours, add subsequently 25 grams of acetylene blacks, stirring at low speed 2 hours, finally adds 400 grams of silica carbon composites, stirring at low speed 2 hours, whipping temp is 25 ℃, and then high speed dispersion 1 hour under the protection of 8 ℃ of cooling waters, obtains stable silicium cathode slurry;
(2) described silicium cathode slurry is coated on to plane copper foil surface, coat weight is 5.26g/cm
2(not containing Copper Foil), the baking oven that is placed in 80 ℃ is dried, and then carrying out roll-in to pole piece thickness is 0.079mm, divides and is cut to the stripe shape pole piece that width is 46mm, makes lithium ion battery silicon cathode pole piece.
The lithium ion battery silicon cathode pole piece that the present embodiment makes comprises collector and is coated in the silicium cathode active material layer on described collector, the material of silicium cathode active material layer comprises silicon materials, binding agent, conductive agent and pore creating material, pore creating material is poly-(carbonic acid 2-fluorine propylene), and described pore creating material accounts for 20% of silicium cathode active material total weight.
To sum up, the lithium ion battery that the embodiment of the present invention third aspect provides energy density after changing into is high and have extended cycle life, and in the situation that other material is identical, energy reserving rate can promote 10～25%, and cycle life can promote 20 ~ 50%.
Claims (10)
1. a lithium ion battery silicon cathode pole piece, it is characterized in that, comprise collector and be coated in the silicium cathode active material layer on described collector, the material of described silicium cathode active material layer comprises silicon materials, binding agent, conductive agent and pore creating material, described pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, and described pore creating material accounts for 5% ~ 25% of silicium cathode active material total weight.
2. a kind of lithium ion battery silicon cathode pole piece as claimed in claim 1, is characterized in that, described pore creating material is one or more the polymer beads at least containing in the polymer of following general formula I,
General formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO
2, CN or halogen, the integer that n is 10 ~ 10000.
3. a kind of lithium ion battery silicon cathode pole piece as claimed in claim 1, is characterized in that, described pore creating material has 500 ~ 1000000 weight average molecular weight.
4. a kind of lithium ion battery silicon cathode pole piece as claimed in claim 1, is characterized in that, described silicon materials are nano silicon particles, aluminosilicate alloy material, silica carbon composite or nano-silicon/silica composite.
5. a kind of lithium ion battery silicon cathode pole piece as claimed in claim 1, is characterized in that, described silicon materials, binding agent and conductive agent account for respectively 60% ~ 90%, 4% ~ 10% and 1% ~ 5% of silicium cathode active material total weight.
6. a kind of lithium ion battery silicon cathode pole piece as claimed in claim 1, is characterized in that, the thickness of described silicium cathode active material layer is 30 ~ 200 μ m.
7. a preparation method for lithium ion battery silicon cathode pole piece, is characterized in that, comprises the following steps:
(1) get silicon materials, binding agent, conductive agent and pore creating material composition silicium cathode slurry solids furnish component, described solid ingredient component is disperseed in organic solvent, stir, make silicium cathode slurry, described pore creating material is the ethylene carbonate of grafting electron withdraw group or the polymer that its homologue forms, and described pore creating material accounts for 5% ~ 25% of described silicium cathode slurry solids furnish component total weight;
(2) described silicium cathode slurry is coated on to collection liquid surface, is dried and roll-in, make lithium ion battery silicon cathode pole piece.
8. a kind of lithium ion battery silicon cathode pole piece as claimed in claim 7, is characterized in that, described pore creating material is one or more the polymer beads at least containing in the polymer of following general formula I,
General formula I:
Wherein, R is the chain-like alkyl of H or C1 ~ C6, and R ' is NO
2, CN or halogen, the integer that n is 10 ~ 10000.
9. a kind of lithium ion battery silicon cathode pole piece as claimed in claim 7, is characterized in that, described pore creating material has 500 ~ 1000000 weight average molecular weight.
10. a lithium ion battery, it is characterized in that, described lithium ion battery is made up of lithium ion battery silicon cathode pole piece, anode pole piece, barrier film, nonaqueous electrolytic solution and shell as described in arbitrary claim in claim 1 ~ 6, and described shell is can open formation or have a housing of air bag.
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| PCT/CN2013/073480 WO2014071717A1 (en) | 2012-11-09 | 2013-03-29 | Silicon negative-electrode plate of lithium ion battery, preparation method therefor, and lithium ion battery |
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| CN105336917A (en) * | 2014-08-14 | 2016-02-17 | 东莞新能源科技有限公司 | Lithium ion battery and its negative electrode sheet preparation method |
| CN105633350A (en) * | 2016-04-01 | 2016-06-01 | 深圳市沃特玛电池有限公司 | Porous pole piece and preparation method thereof and lithium ion battery |
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|---|---|
| WO2014071717A1 (en) | 2014-05-15 |
| CN103811719B (en) | 2016-11-23 |
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