CN104934606A - Silicon-based composite material and preparation method and application thereof - Google Patents
Silicon-based composite material and preparation method and application thereof Download PDFInfo
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- CN104934606A CN104934606A CN201510250604.6A CN201510250604A CN104934606A CN 104934606 A CN104934606 A CN 104934606A CN 201510250604 A CN201510250604 A CN 201510250604A CN 104934606 A CN104934606 A CN 104934606A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M4/137—Electrodes based on electro-active polymers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application discloses a silicon-based composite material which comprises a silicon-based material, wherein the surface of the silicon-based material is modified by an organosilicon compound containing amino and/or carboxyl. The silicon-based composite material is applied to a lithium ion secondary battery, during a battery cycle process, the pulverization of an electrode membrane can be effectively relieved, and battery stability can be improved. When the silicon-based composite material is used with a carboxylic acid binding agent, a polycarboxylate binding agent or a polyimide binding agent in a matching way, hydrogen bonds can be formed by the silicon-based composite material and a polymer in the bonding agent, the adhesion force is enhanced, the incapability of the silicon-based material in contact with the binding agent and a conductive agent due to volume expansion/contraction during the battery cycle process is prevented, and therefore, energy density and cycle performance of the lithium ion secondary battery are effectively improved.
Description
Technical field
The application relates to a kind of silicon based composite material and preparation method thereof, and applies composite sheet and the lithium ion battery of this silicon based composite material, belongs to technical field of lithium ion.
Background technology
At present, business-like anode of lithium ion battery active material mainly graphite.But, graphite due to specific discharge capacity limited, volume and capacity ratio room for promotion is little, take graphite as the user demand that the lithium ion battery of active material of positive electrode cannot meet following high power capacity, small size electronic equipment.
By research, it is found that as lithium ion battery anode material, the most promising is silicon.The theoretical gram volume of silica-base material is up to 4200mAh/g, and theoretical volume specific capacity is up to 7200mAh/cm
3.But silica-base material is in the process of de-/embedding lithium, and the change in volume of active material particle is comparatively large, easily breaks, coming off causes the efflorescence of electrode film, thus make the cycle performance of lithium ion battery worsen, limit the commercial applications of lithium ion battery.
In view of this, ensureing the good contact with binding agent and conductive agent after the granule integrity of silica-base material in charge and discharge process and circulation, is the key of raising cycle performance of lithium ion battery.
Summary of the invention
According to an aspect of the application, provide a kind of silicon based composite material, this silicon based composite material, in circulating battery process, effectively can alleviate the efflorescence of electrode film, effectively improves the stability of lithium rechargeable battery.
Described silicon based composite material, is characterized in that, the surface of silica-base material is through modified with organosilicon compounds; Described organo-silicon compound contain at least one in amino or carboxyl.
Described amino is selected from-NH
2,-NHR ,-NR
2in at least one; Wherein R is alkyl.
Described carboxyl is-COOH.
Preferably, described organo-silicon compound are selected from least one in the compound with structural formula shown in formula I, the compound with structural formula shown in formula II:
Wherein, R
1hydrogen or R
1be selected from the alkyl of carbon number 1 ~ 10; R
2hydrogen or R
2be selected from the alkyl of carbon number 1 ~ 10; R
3hydrogen or R
3be selected from the alkyl of carbon number 1 ~ 10; R
4be selected from carbon number 1 ~ 20 and contain group that is amino and/or carboxyl;
Wherein, R
5be selected from carbon number 1 ~ 20 and contain group that is amino and/or carboxyl; R
6hydrogen or R
6be selected from the alkyl of carbon number 1 ~ 10; R
7hydrogen or R
7be selected from the alkyl of carbon number 1 ~ 10; R
8hydrogen or R
8be selected from the alkyl of carbon number 1 ~ 10.
Preferably, R in formula I
1be selected from hydrogen, methyl, ethyl or isopropyl; R
2be selected from hydrogen, methyl, ethyl or isopropyl; R
3be selected from hydrogen, methyl, ethyl or isopropyl; R
4be selected from carbon number 1 ~ 15 and contain group that is amino and/or carboxyl.
Preferably, R in formula II
5be selected from carbon number 1 ~ 15 and contain group that is amino and/or carboxyl; R
6be selected from hydrogen, methyl, ethyl or isopropyl; R
7be selected from hydrogen, methyl, ethyl or isopropyl; R
8be selected from hydrogen, methyl, ethyl or isopropyl.
Preferably, described organo-silicon compound are selected from the compound with structural formula shown in formula I.In formula I, organo-silicon compound have higher chemical stability, and through its silica-base material doing modification in battery, cyclical stability is higher.
Described containing group that is amino and/or carboxyl, at least one hydrogen atom on hydrocarbon molecules is by after amino and/or carboxyl substituted, then lose the group of arbitrary hydrogen atom formation.
Described alkyl is any linear paraffin molecule, the alkane molecule containing arbitrarily side chain or any naphthene hydrocarbon molecule, loses the group that arbitrary hydrogen atom obtains.
Preferably, described organo-silicon compound are selected from 3-aminopropyl triethoxysilane, to anilino-three isopropoxy silane, 4-butylbenzene amido trimethoxy silane, succinic acid trimethoxy esters of silicon acis, 4-M-phthalic acid ethyl triethoxy silicane alkane, 4-butylamine triethoxysilane, 2-malonic acid trimethoxy silane, 4-phenetidine triethoxy esters of silicon acis, 5-(3,3-diacetoxyl) valeric acid triethoxysilane, at least one in (3,5-dimethylamino)-benzene ethyoxyl trimethoxy esters of silicon acis.
Described silica-base material comprises elementary silicon, silicon/carbon composite, silicon-base oxide SiO
x, at least one in silicon-base alloy.
According to the another aspect of the application, provide the method preparing above-mentioned silicon based composite material, the method is simple to operate, with low cost, is applicable to large-scale industrial production.
Prepare the method for described silicon based composite material, it is characterized in that, after being contacted with the system containing organo-silicon compound by silica-base material, drying obtains described silicon based composite material.Described contact includes but not limited to dipping, vapour deposition.
The method of described drying includes but not limited to filter post-drying, spraying dry.
Preferably, described silica-base material is be impregnated in by silica-base material in the solution containing organo-silicon compound with the system way of contact containing organo-silicon compound.
Preferably, described containing in the solution of organo-silicon compound, the concentration of organo-silicon compound is 0.1mol/L ~ 5mol/L.Preferably, the upper limit of concentration of described organo-silicon compound is optionally from 5mol/L, 4mol/L, 3mol/L, and lower limit is optionally from 0.2mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 2mol/L.Further preferably, the concentration of described organo-silicon compound is 0.5mol/L ~ 5mol/L.
Preferably, described silica-base material is 20 ~ 90 DEG C with the system Contact Temperature containing organo-silicon compound.Further preferably, described silica-base material is selected from 90 DEG C, 80 DEG C, 70 DEG C, 60 DEG C, 50 DEG C with the system Contact Temperature range limit containing organo-silicon compound, and lower limit is selected from 20 DEG C, 30 DEG C, 40 DEG C.
Preferably, described silica-base material is 1 ~ 10 hour with the system time of contact containing organo-silicon compound.Further preferably, described silica-base material be selected from 10 hours containing system upper limit time of contact of organo-silicon compound, 7 hours, lower limit is selected from 1 hour, 5 hours.
Preferably, described silica-base material contacts under catalyst existence condition with the system containing organo-silicon compound; Described catalyst is selected from least one in acid, alkali, metal-organic complex.
Described acid comprises inorganic acid and organic acid.Preferably, described acid is selected from least one in hydrochloric acid, nitric acid, phytic acid, citric acid.
Described alkali comprises inorganic base and organic base.Preferably, described alkali is selected from least one in NaOH, triethylamine, pyridine.
Preferably, described metal-organic complex is selected from dibutyltin diacetate and/or tetra isopropyl titanate.
As a kind of execution mode of the application, prepare the method for described silicon based composite material, it is characterized in that, after silica-base material contacts with the system containing organo-silicon compound, after drying, heat treatment, obtain described silicon based composite material.
Preferably, described heat treated temperature is 100 ~ 500 DEG C.Further preferably, the described heat-treatment temperature range upper limit is selected from 500 DEG C, 400 DEG C, 300 DEG C, and lower limit is selected from 100 DEG C, 120 DEG C, 150 DEG C, 200 DEG C, 270 DEG C.
Preferably, the described heat treated time is 3 ~ 15 hours.
In above-mentioned preferred heat treatment temperature with under the time, thermal effectiveness is more excellent, and efficiency is higher, is more conducive to the decomposition avoiding organosilicon material simultaneously.
According to the another aspect of the application, a kind of negative plate is provided, it is characterized in that, containing above-mentioned arbitrary silicon based composite material and/or the silicon based composite material for preparing according to above-mentioned either method.
Preferably, described negative plate is by obtaining the slurry formed containing described silicon based composite material, conductive agent and binding agent coating on a current collector.
Preferably, in described binding agent containing being polymerized by least one in carboxylic acid compound monomer, carboxylic acid ester compound monomer, aminated compounds monomer the polymer formed.Described silicon based composite material and polycarboxylic acid binding agent, polycarboxylate class binding agent or polyimide binding agent with the use of, bonding force can be strengthened by the hydrogen bond formed with polymer in binding agent, avoid silica-base material in circulating battery process to lose and the contacting of binding agent and conductive agent because of volumetric expansion/contraction, thus effectively improve energy density and the cycle performance of lithium rechargeable battery.
Preferably, prepare in the binding agent that electrode slice uses, containing being polymerized by least one in acrylic monomer, acrylic ester monomer, acid imide monomer the polymer formed.
Preferably, described acrylic monomer is selected from least one in the compound with chemical formula shown in formula III:
Wherein, R
9hydrogen or R
9be selected from the alkyl that carbon number is 1 ~ 20.
Preferably, described acrylic ester monomer is selected from least one in the compound with chemical formula shown in formula IV:
Wherein, R
10hydrogen or R
10be selected from the alkyl that carbon number is 1 ~ 20; R
11be selected from the alkyl that carbon number is 1 ~ 20.
Preferably, described acid imide monomer is selected from least one in the compound with chemical formula shown in formula V:
Wherein, R
12hydrogen or R
12be selected from the alkyl that carbon number is 1 ~ 20; R
13hydrogen or R
13be selected from the alkyl that carbon number is 1 ~ 20; R
14hydrogen or R
14be selected from the alkyl that carbon number is 1 ~ 20.
Further preferably, at least one in polyacrylic acid (being abbreviated as PAA), polymethyl methacrylate (being abbreviated as PMMA), polyimides (being abbreviated as PI) is contained in described binding agent.
According to the another aspect of the application, a kind of lithium ion battery is provided, it is characterized in that, containing above-mentioned arbitrary negative plate.
Preferably, described lithium ion battery is coiled lithium ion battery or stack type lithium ion battery.
The beneficial effect that the application can produce at least comprises:
(1) silicon based anode material that provides of the application, has good tack, effectively can alleviate the efflorescence of silica-base material in cyclic process itself, for lithium ion battery, effectively can improve the stability of lithium rechargeable battery between particle.
(2), there is chemical bond between silicon based composite material and binding agent used, significantly can strengthen the structural stability of negative plate in the negative plate that provides of the application.For lithium ion battery, energy density and the cycle performance of lithium rechargeable battery effectively can be improved.
(3) the silicon based composite material preparation method that provides of the application, is simple and easy to implement and with low cost, is easy to large-scale industrial production.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiments.
In embodiment, 3-aminopropyl triethoxysilane, to anilino-three isopropoxy silane, 4-butylbenzene amido trimethoxy silane, succinic acid trimethoxy esters of silicon acis, 4-M-phthalic acid ethyl triethoxy silicane alkane, 4-butylamine triethoxysilane, 2-malonic acid trimethoxy silane, 4-phenetidine triethoxy esters of silicon acis, 5-(3,3-diacetoxyl) valeric acid triethoxysilane, (3,5-dimethylamino)-benzene ethyoxyl trimethoxy esters of silicon acis is purchased from Nanjing Chen Gong organosilicon material Co., Ltd.
In embodiment, silicon-base oxide is SiO
x, 0 < x < 2, number average bead diameter (D50) is 2-7 μm; Carbon coated Si powder number average bead diameter (D50) is 0.5-5 μm; Carbon coated Si/C number average bead diameter (D50) is 5-20 μm; Carbon coated Si ferroalloy SiFe number average bead diameter (D50) is 0.2-2 μm.
In embodiment, polyacrylic acid (being abbreviated as PAA) purchased from Sigma-Aldrich (Sigma-Aldrich), number-average molecular weight 50-80w; Polymethyl methacrylate (being abbreviated as PMAA) purchased from Sigma-Aldrich, number-average molecular weight 30-50w; Polyimides (being abbreviated as PI) purchased from Shin-Etsu Chemial Co., Ltd (ShinEtsu), number-average molecular weight 8-10w.
If no special instructions, the number in embodiment is mass fraction.
Embodiment 1
the preparation of silicon based composite material A1:
Be in the anhydrous tetrahydrofuran solution of 1mol/L by the SiOx powder dispersion of 100 mass parts in the 3-aminopropyl triethoxysilane concentration of 1000 mass parts.Gained suspension, under constantly stirring, adds the dibutyltin diacetate of 0.1 mass parts and the water of 1 mass parts, reacts after 5 hours, the solid arrived by collecting by filtration, process 3 hours, obtain described silicon based composite material, be designated as A1 at being placed in 500 DEG C at 20 DEG C.
negative plate N1 makes:
Be dissolved in the water of 110 mass parts by the polyacrylic acid (being abbreviated as PAA) of 5 mass parts, add obtained A1, the conductive agent acetylene black of 5 mass parts, mixes, obtains cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2, carry out after forced air drying 20h subsequently colding pressing at 85 DEG C, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N1.
positive plate P1 makes:
Positive electrode active materials cobalt acid lithium, conductive agent conductive black Super-P, binding agent polyvinylidene fluoride (are abbreviated as PVDF, in binding agent, the mass percentage of polyvinylidene fluoride is 10%) be uniformly dispersed in solvent N-methyl pyrilidone (being abbreviated as NMP), make anode sizing agent.In anode sizing agent, solids content is 75wt%, comprises the conductive black Super-P of the nickle cobalt lithium manganate of 96wt%, PVDF and 2wt% of 2% in solid constituent.Anode sizing agent being coated on equably thickness is on the plus plate current-collecting body aluminium foil of 16 μm, and solid coating weight is 0.018g/cm
2.After drying at 85 DEG C, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 85 DEG C of vacuum conditions, soldering polar ear, gained positive plate is designated as P1
#.
the preparation of lithium rechargeable battery C1:
Barrier film is the polypropylene film of 12 μm.
Electrolyte is by non-aqueous organic solvent and LiPF
6composition, LiPF
6weight percentage is in the electrolytic solution 8%.Non-aqueous organic solvent is made up of according to weight ratio 8: 85: 5: 2 ethylene carbonate, diethyl carbonate, methyl ethyl carbonate and ethenylidene carbonic ester.
Positive plate P1, barrier film, negative plate N1 are folded in order, makes barrier film be in the effect playing isolation in the middle of positive anode, be then wound into the square naked battery core that thickness is 8mm, width is 60mm, length is 130mm.Naked battery core is loaded aluminum foil sack, vacuum bakeout 10h at 75 DEG C, inject electrolyte, carry out changing into aging after Vacuum Package, namely complete the preparation of lithium rechargeable battery, gained lithium rechargeable battery is designated as C1.
Embodiment 2
the preparation of silicon based composite material A2:
Be in the anhydrous methylene chloride solution of 1.2mol/L in 500 mass parts to anilino-three isopropoxy silane concentration by the SiOx powder dispersion of 100 mass parts.Gained suspension is heated to 40 DEG C under constantly stirring, and adds the pyridine of 1 mass parts and the water of 5 mass parts, reacts after 7 hours at 40 DEG C, by the solid adopting spray drying process to collect, process 5 hours at being placed in 300 DEG C, obtain described silicon based composite material, be designated as A2.
negative plate N2 makes:
Be dissolved in the water of 110 mass parts by the polyacrylic acid (being abbreviated as PAA) of 5 mass parts, add obtained A2, the conductive agent acetylene black of 5 mass parts, mixes, obtains cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2, at 85 DEG C after forced air drying 20h, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N2.
the making of battery C2:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N2 into, and gained lithium rechargeable battery is designated as C2.
Embodiment 3
the preparation of silicon based composite material A3:
Be in the toluene solution of 2mol/L in 1000 mass parts to anilino-three isopropoxy silane concentration by the SiOx powder dispersion of 100 mass parts, add the water of 10 mass parts.Gained suspension is heated to 90 DEG C under constantly stirring, and reacts after 10 hours at 90 DEG C, by the solid adopting spray drying process to collect, processes 15 hours, obtain described silicon based composite material, be designated as A3 at being placed in 100 DEG C.
negative plate N3 makes:
Be dissolved in the water of 110 mass parts by the polymethyl methacrylate (being abbreviated as PMAA) of 5 mass parts, add obtained A3, the conductive agent acetylene black of 5 mass parts, mixes, obtains cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2, at 85 DEG C after forced air drying 20h, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N3.
the making of battery C3:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N3 into, and gained lithium rechargeable battery is designated as C3.
Embodiment 4
the preparation of silicon based composite material A4:
Be in the ethyl acetate solution of 0.8mol/L by the SiOx powder dispersion of 100 mass parts in the succinic acid trimethoxy esters of silicon acis concentration of 2000 mass parts.Gained suspension adds the tetra isopropyl titanate of 1 mass parts and the water of 2 mass parts, under constantly stirring, reacts after 10 hours at 50 DEG C, by the solid adopting spray drying process to collect, process 3 hours at being placed in 200 DEG C, obtain described silicon based composite material, be designated as A4.
negative plate N4 makes:
Be dissolved in the NMP of 110 mass parts by the polyimides (being abbreviated as PI) of 5 mass parts, add obtained A4, the conductive agent acetylene black of 5 mass parts, mixes, obtains cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2.Forced air drying 20h, heat treatment after 3 hours at 300 DEG C at 85 DEG C, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N4.
the making of battery C4:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N4 into, and gained lithium rechargeable battery is designated as C4.
Embodiment 5
the preparation of silicon based composite material A5:
Be in the aqueous solution of 0.1mol/L by the carbon coated Si/C powder dispersion of 100 mass parts in the 4-M-phthalic acid ethyl triethoxy silicane alkane concentration of 1000 mass parts.Gained suspension, under constantly stirring, reacts after 7 hours at 60 DEG C, adopts spray drying process to collect solid, obtains described silicon based composite material, be designated as A5.
negative plate N5 makes:
Be dissolved in the NMP of 110 mass parts by the polyimides (being abbreviated as PI) of 5 mass parts, add obtained A5, the conductive agent acetylene black of 5 mass parts, mixes, obtains cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2.Forced air drying 20h, heat treatment after 3 hours at 300 DEG C at 85 DEG C, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N5.
the making of battery C5:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N5 into, and gained lithium rechargeable battery is designated as C5.
Embodiment 6
the preparation of silicon based composite material A6:
Be in the ethanolic solution of 0.2mol/L by the carbon coated Si/C powder dispersion of 100 mass parts in the 4-butylamine triethoxysilane concentration of 800 mass parts.Gained suspension adds the NaOH of 1 mass parts and the water of 20 mass parts, under constantly stirring, reacts after 7 hours at 70 DEG C, by the solid adopting spray drying process to collect, process 5 hours at being placed in 150 DEG C, obtain described silica-based composite active material, be designated as A6.
negative plate N6 makes:
The PMAA of 5 mass parts is dissolved in the water of 110 mass parts, adds the conductive agent acetylene black of obtained A6,5 mass parts, mix, obtain cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2.Forced air drying 20h, heat treatment after 3 hours at 300 DEG C at 85 DEG C, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N6.
the making of battery C6:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N6 into, and gained lithium rechargeable battery is designated as C6.
Embodiment 7
the preparation of silicon based composite material A7:
Be in the aqueous solution of 5mol/L by the carbon coated Si powder dispersion of 100 mass parts in the 2-malonic acid trimethoxy silane concentration of 1200 mass parts.Gained suspension adds the phytic acid of 2 mass parts, and under constantly stirring, react after 10 hours at 80 DEG C, solid collected by filtration, namely drying obtains described silicon based composite material, is designated as A7.
negative plate N7 makes:
The PI of 5 mass parts is dissolved in the NMP of 110 mass parts, adds the conductive agent acetylene black of obtained A7,5 mass parts, mix, obtain cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2.Forced air drying 20h, heat treatment after 3 hours at 300 DEG C at 85 DEG C, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N7.
the making of battery C7:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N7 into, and gained lithium rechargeable battery is designated as C7.
Embodiment 8
the preparation of silicon based composite material A8:
Be in the aqueous solution of 3mol/L by the carbon coated Si powder dispersion of 100 mass parts in the 4-ethoxy aniline triethoxy esters of silicon acis concentration of 1500 mass parts.Gained suspension adds the triethylamine of 3 mass parts, under constantly stirring, reacts after 1 hour, the solid arrived by collecting by filtration, process 3 hours, obtain described silicon based composite material, be designated as A8 at being placed in 270 DEG C at 80 DEG C.
negative plate N8 makes:
The PMAA of 5 mass parts is dissolved in the water of 110 mass parts, adds the conductive agent acetylene black of obtained A7,5 mass parts, mix, obtain cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2.Forced air drying 20h, heat treatment after 3 hours at 300 DEG C at 85 DEG C, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N8.
the making of battery C8:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N8 into, and gained lithium rechargeable battery is designated as C8.
Embodiment 9
the preparation of silicon based composite material A9:
Be in the aqueous solution of 1.5mol/L by the carbon coated Si Fe powder dispersion of 100 mass parts in 5-(3,3-diacetoxyl) the valeric acid triethoxysilane concentration of 1000 mass parts.Gained suspension constantly stirs down, and react after 1 hour at 50 DEG C, the solid that collecting by filtration arrives, namely drying obtains described silicon based composite material, is designated as A9.
negative plate N9 makes:
The PI of 5 mass parts is dissolved in the NMP of 110 mass parts, adds the conductive agent acetylene black of obtained A9,5 mass parts, mix, obtain cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2.Forced air drying 20h, heat treatment after 3 hours at 300 DEG C at 85 DEG C, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N9.
the making of battery C9:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N9 into, and gained lithium rechargeable battery is designated as C9.
Embodiment 10
the preparation of silicon based composite material A10:
Be in the aqueous solution of 0.5mol/L by the carbon coated Si Fe powder dispersion of 100 mass parts in (3,5-dimethylamino)-benzene ethyoxyl trimethoxy esters of silicon acis concentration of 1200 mass parts.Add the tetra isopropyl titanate of 2 mass parts in gained suspension, under constantly stirring, react at 90 DEG C after 1 hour, the solid that collecting by filtration is arrived, process 3 hours at being placed in 120 DEG C, obtain described silica-based composite active material, be designated as A10.
negative plate N10 makes:
The PAA of 5 mass parts is dissolved in the water of 110 mass parts, adds the conductive agent acetylene black of obtained A10,5 mass parts, mix, obtain cathode size.Cathode size being coated on equably thickness is on the negative current collector Copper Foil of 12 μm, and solid coating weight is 0.0089g/cm
2.Forced air drying 20h, heat treatment after 3 hours at 300 DEG C at 85 DEG C, carry out colding pressing, trimming, cut-parts, itemize, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, gained negative film is designated as N10.
the making of battery C10:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N10 into, and gained lithium rechargeable battery is designated as C10.
Embodiment 11
negative plate N11 makes:
As embodiment 10 uses A10 to make cathode pole piece, difference is not use PAA in pole piece manufacturing process, and uses the CMC of the SBR of 3 mass parts and 2 mass parts as bonding agent.
the making of battery C11:
Other steps are identical with the making of C1, and difference is, negative plate N1 changes negative plate N11 into, and gained lithium rechargeable battery is designated as C11.
Comparative example 1
Concrete step and pulp furnish are with embodiment 1, and difference is, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the SiOx powder of 100 mass parts, the lithium ion battery of gained is designated as DC1.
Comparative example 2
Concrete step and pulp furnish, with embodiment 4, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the SiOx powder of 100 mass parts, the lithium ion battery of gained is designated as DC2.
Comparative example 3
Concrete step and pulp furnish, with embodiment 6, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the carbon coated Si/C powder of 100 mass parts, the lithium ion battery of gained is designated as DC3.
Comparative example 4
Concrete step and pulp furnish, with embodiment 5, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the carbon coated Si/C powder of 100 mass parts, the lithium ion battery of gained is designated as DC4.
Comparative example 5
Concrete step and pulp furnish, with embodiment 8, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the carbon coated Si powder of 100 mass parts, the lithium ion battery of gained is designated as DC5.
Comparative example 6
Concrete step and pulp furnish, with embodiment 7, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the carbon coated Si powder of 100 mass parts, the lithium ion battery of gained is designated as DC6.
Comparative example 7
Concrete step and pulp furnish, with embodiment 10, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the carbon coated Si Fe powder of 100 mass parts, the lithium ion battery of gained is designated as DC7.
Comparative example 8
Concrete step and pulp furnish, with embodiment 9, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the carbon coated Si Fe powder of 100 mass parts, the lithium ion battery of gained is designated as DC8.
Comparative example 9
Concrete step and pulp furnish, with embodiment 11, do not have silicon based composite material preparation process, and when making negative plate, directly replace silicon based composite material with the carbon coated Si Fe powder of 100 mass parts, the lithium ion battery of gained is designated as DC9.
In embodiment 1 ~ 11, comparative example 1 ~ 9 numbering of battery and manufacturing conditions as shown in table 1.
Table 1
Embodiment 12
Test the circulation volume conservation rate of battery C1 ~ C11, DC1 ~ DC9 and expansion of anode sheet rate respectively, concrete grammar is:
Often kind of battery gets 4 respectively, at normal temperatures with 0.7C constant current charge to 4.3V, again with 4.3V constant-potential charge to electric current for 0.05C, after leaving standstill half an hour, with the constant current of 0.5C to battery discharge to 3.0V, this is a charge and discharge cycles process, and this discharge capacity is the discharge capacity of first time circulation.Lithium rechargeable battery is carried out cycle charge discharge electrical testing in a manner described, records the discharge capacity of circulation 100 weeks, 200 weeks, 300 weeks, 400 weeks and 500 weeks respectively.After circulation in 500 weeks, disassemble the thickness of battery measurement anode strip.
Discharge capacity × 100% of discharge capacity/the first in the capability retention=the N week in battery N week week.
Thickness swelling after anode strip N week=(thickness-fresh anode sheet thickness after N week circulation)/fresh anode sheet thickness × 100%.
Result is as shown in table 2.
The different battery of table 2 is through the capability retention of 500 circulations
As can be seen from the data in table 2, adopt the battery C1 ~ C11 of technical scheme, after 500 circulations, battery capacity conservation rate will far above the battery DC1 ~ DC9 not adopting technical scheme, and the volumetric expansion of C1 ~ C11 also will far below DC1 ~ DC9.Show through surface modification treatment, the adhesion of silicon based composite material and binding agent is strengthened, and by suppressing the entirety bounce-back of electrochemistry cyclic process middle-jiao yang, function of the spleen and stomach pole piece, avoiding coming off of active material, thus significantly improving cycle performance and the stability of lithium ion battery.The data of contrast D9 and other Battery pack can be found out, when not adopting polycarboxylic acid and polyimide binding agent, because between SBR bonding agent and silicon materials, adhesion is too poor, and battery performance extreme degradation.But when carrying out silane-modified process to silicon materials surface, battery C11 performance still can be greatly improved.Illustrate that silane-modified process can increase the intergranular tack of silicon materials, alleviate the expands active material that causes of cyclic process Anodic active material volume and to come off and pole piece rebounds.
The foregoing is only the preferred embodiment of the application, be not limited to the application, for a person skilled in the art, the application can have various modifications and variations.Within all spirit in the application and principle, any amendment done, equivalent replacement, improvement etc., within the protection range that all should be included in the application.
Claims (10)
1. a silicon based composite material, comprises silica-base material, it is characterized in that, the surface of described silica-base material is through modified with organosilicon compounds; Described organo-silicon compound contain amino and/or carboxyl.
2. silicon based composite material according to claim 1, is characterized in that, described organo-silicon compound are selected from least one in the compound with structural formula shown in formula I, the compound with structural formula shown in formula II:
Wherein, R
1hydrogen or R
1be selected from the alkyl of carbon number 1 ~ 10; R
2hydrogen or R
2be selected from the alkyl of carbon number 1 ~ 10; R
3hydrogen or R
3be selected from the alkyl of carbon number 1 ~ 10; R
4be selected from carbon number 1 ~ 20 and contain group that is amino and/or carboxyl;
Wherein, R
5be selected from carbon number 1 ~ 20 and contain group that is amino and/or carboxyl; R
6hydrogen or R
6be selected from the alkyl of carbon number 1 ~ 10; R
7hydrogen or R
7be selected from the alkyl of carbon number 1 ~ 10; R
8hydrogen or R
8be selected from the alkyl of carbon number 1 ~ 10.
3. silicon based composite material according to claim 1, it is characterized in that, described organo-silicon compound are selected from 3-aminopropyl triethoxysilane, to anilino-three isopropoxy silane, 4-butylbenzene amido trimethoxy silane, succinic acid trimethoxy esters of silicon acis, 4-M-phthalic acid ethyl triethoxy silicane alkane, 4-butylamine ethyl triethoxy silicane alkane, 2-malonic acid trimethoxy silane, 4-phenetidine ethyl triethoxy silicane acid esters, 5-(3, 3-diacetoxyl) valeric acid triethoxysilane, (3, 5-dimethylamino) at least one in-benzene ethyoxyl trimethoxy esters of silicon acis.
4. prepare the method for silicon based composite material described in claim 1, it is characterized in that, after being contacted with the system containing organo-silicon compound by silica-base material, drying obtains described silicon based composite material.
5. the method for silicon based composite material according to claim 4, is characterized in that, described silica-base material is be impregnated in by silica-base material in the solution containing organo-silicon compound with the system way of contact containing organo-silicon compound; Described containing in the solution of organo-silicon compound, the concentration of organo-silicon compound is 0.1mol/L ~ 5mol/L, is preferably 0.5mol/L ~ 5mol/L.
6. the method for silicon based composite material according to claim 4, is characterized in that, described silica-base material is 20 ~ 90 DEG C with the system Contact Temperature containing organo-silicon compound.
7. the method for silicon based composite material according to claim 4, it is characterized in that, described silica-base material contacts under catalyst existence condition with the system containing organo-silicon compound; Described catalyst is selected from least one in acid, alkali, metal-organic complex.
8. a negative plate, is characterized in that, containing the silicon based composite material described in any one of claim 1-3 and/or method prepares according to any one of claim 4-7 silicon based composite material.
9. negative plate according to claim 8, is characterized in that, prepares in the binding agent that described negative plate uses, containing being polymerized by least one in acrylic monomer, acrylic ester monomer, acid imide monomer the polymer formed.
10. a lithium ion battery, is characterized in that, containing negative plate according to claim 8.
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