CN103855368B - Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery - Google Patents

Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery Download PDF

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CN103855368B
CN103855368B CN201210498890.4A CN201210498890A CN103855368B CN 103855368 B CN103855368 B CN 103855368B CN 201210498890 A CN201210498890 A CN 201210498890A CN 103855368 B CN103855368 B CN 103855368B
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secondary battery
negative electrode
lithium
lithium ionic
ion secondary
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CN103855368A (en
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廖华栋
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 negative electrode of lithium ionic secondary battery, for carbon-coating is coated on the core-shell structure copolymer clad structure of silicon alloy core surface formation, silicon alloy kernel chemical expression is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c is 1% ~ 50%, d is one or more that 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr, and carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.This negative electrode of lithium ionic secondary battery has excellent cycle performance and efficiency first.The embodiment of the present invention additionally provides preparation method, the cathode pole piece of lithium ion secondary battery of negative electrode of lithium ionic secondary battery, and lithium rechargeable battery, and this lithium rechargeable battery energy density is high and cycle performance is good.

Description

Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery
Technical field
The present invention relates to field of lithium ion secondary, particularly relate to a kind of negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery.
Background technology
Along with the fast development of mancarried electronic aid and electric automobile, the demand of people to the lithium rechargeable battery with high-energy-density and excellent cycle performance becomes more urgent.
Negative material mainly graphite and the material with carbon element of current commercial lithium rechargeable battery, research and practice show, the electrochemistry capacitance of material with carbon element is low, and its theoretical capacity is only 372mAh/g, and volume and capacity ratio is quite limited, can not practical requirement.In recent years, more research is absorbed in and is found metal and alloy type material as new and effective storage lithium titanate cathode material system, and such as silicon has very high specific capacity (4200mAh/g), and the volume and capacity ratio theoretical value of silicon is up to 7200mAh/cm 3, be 10 times of material with carbon element volume and capacity ratio, therefore now become the main flow negative material studied in the world.The alloy cpd of silicon generally includes silicon, aluminium and transition elements etc., such as, alloy Si in the US7851085B2 patent that 3M Innovative Properties Company provides aal bt csn dm eli f, a, b, c, d, e and f represent atomic percentage respectively, and wherein (1) Si accounts for molar fraction is 35% ~ 70%; (2) Al accounts for molar fraction is 1% ~ 45%; (3) transition metal T accounts for molar fraction is 5% ~ 25%; (4) Sn accounts for molar fraction is 1% ~ 15%; (5) M represents one or more combinations in yttrium, lanthanide series, actinides, accounts for 2% ~ 15% of molar fraction.The cyclical stability of lithium rechargeable battery can be improved to a certain extent when this alloy is for making lithium rechargeable battery, but because being subject to specific volume quantitative limitation, it still easily occurs that volumetric expansion change causes greatly lithium rechargeable battery internal structure to be destroyed in the process of removal lithium embedded, and, silicon in alloy type composite material can be exposed in electrolyte, silicon face will form unstable electrolyte passivating film, finally cause chemical property deterioration, cycle performance reduction and lithium rechargeable battery inefficient problem first.
The storage lithium theoretical specific capacity of germanium is 1700mAh/g, and the diffusion velocity of lithium ion in germanium is 400 times in silicon.Existing researcher gives the report of germanium for the preparation of bianry alloys such as Ge-Cu, Ge-Sb and Ge-Co at present, but these germanic bianry alloys are generally single stable alloy phase, and germanium component content is wherein high, and cost is larger.So far, the germanium-containing alloy more than ternary and ternary is comparatively rare.In preparation method, germanic bianry alloy many employings physical sputtering, electro-deposition or high energy ball mill method, but it is the alloy firm of several μm that physical sputtering and electro-deposition method etc. are only limitted to make thickness, seriously limit the volume energy density of lithium rechargeable battery, the alloy product that high energy ball mill method obtains may be even not, and then will affect the performance of lithium rechargeable battery.
Given this, the germanic negative active core-shell material that can improve lithium rechargeable battery cycle performance and efficiency first of development of new seems very important as early as possible.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of negative electrode of lithium ionic secondary battery, in order to improve cycle performance and the efficiency first of existing negative active core-shell material.Embodiment of the present invention second aspect provides the preparation method of described negative electrode of lithium ionic secondary battery.The embodiment of the present invention third aspect provides the cathode pole piece of lithium ion secondary battery comprising described negative electrode of lithium ionic secondary battery, and embodiment of the present invention fourth aspect provides the lithium rechargeable battery comprising described negative electrode of lithium ionic secondary battery, this lithium rechargeable battery energy density is high and cycle performance is good.
First aspect, embodiments provide a kind of negative electrode of lithium ionic secondary battery, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
Preferably, a is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
Preferably, by mass fraction, carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
Preferably, the particle diameter of silicon alloy kernel is 10 ~ 30 μm.
A kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention first aspect provides is novel composite material, silicon alloy kernel is wherein polynary negative active core-shell material, Si and Al is basic phase, Sn and transition metal Co, Ni, Ti, Fe, Cu, Mn, Mo, the volumetric expansion that the Si that V and Cr can cushion height ratio capacity to a certain extent occurs when lithium rechargeable battery discharge and recharge, Ge is introduced in the specific capacity and conductivity that improve this negative electrode of lithium ionic secondary battery to a certain extent, and, the coated carbon-coating of silicon alloy core surface effectively can avoid silicon and electrolyte generation side reaction.This negative electrode of lithium ionic secondary battery has excellent cycle performance and efficiency first.
Second aspect, embodiments provides a kind of preparation method of negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al and M, according to chemical expression be: Si age bal cm dproportioning is mixed to form mixture, and a, b, c and d represent molar fraction respectively, and a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more;
(2) described mixture is placed in electric arc induction furnace, melting at 800 ~ 1000 DEG C of temperature under vacuum or argon shield condition, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, under vacuum or argon shield condition at 800 ~ 1000 DEG C of temperature secondary smelting, become thin slice or bulk by melt-quenching method preparation, carry out ball milling subsequently and obtain pulverous silicon alloy kernel;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 400 ~ 1000 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and carbon source, argon gas and carbon source total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described carbon source accounts for 10% ~ 30% of argon gas and carbon source cumulative volume, heats up and keeps in-furnace temperature to be 400 ~ 1000 DEG C of reaction 5 ~ 40min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
In the step (2) of the embodiment of the present invention, the temperature of twice melting is 800 ~ 1000 DEG C, in this temperature range, impurity in raw metal such as metal oxide generation deoxygenation can be reduced, to improve the purity of target product, and can ensure that a large amount of evaporations does not occur metallic element, therefore can the chemical composition of goal of regulation and control product comparatively accurately.Preferably, smelting temperature is 900 ~ 950 DEG C.Preferably, under argon gas atmosphere, air pressure is 0.1 ~ 0.2MPa.
" being cast into ingot casting subsequently " in the present invention is conventional cooling and casting, in order to the product completing first time melting is made target shape and size.Have the ingot casting of target shape and size and " become thin slice or bulk by melt-quenching method preparation " subsequently, this process is conventional quick cooling and casting, in order to thin slice or the bulk of crystal structure during obtained maintenance chilling temperature.Described target shape and size are not limit, and its object is only that the product after by pill heat is cast into the ingot casting being convenient to secondary smelting of small volume.
Preferably, a is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
Preferably, by mass fraction, carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
Preferably, the particle diameter of silicon alloy kernel is 10 ~ 30 μm.
The step (3) of the embodiment of the present invention is coated for adopting chemical vapour deposition technique to carry out carbon-coating to silicon alloy kernel, thus the silicon solved in silicon alloy kernel will generate the problem of electrolyte passivating film in electrolyte generation side reaction.
Preferably, described carbon source is selected from carbon atom number is one in alkane, the carbon atom number alkene that is 1 ~ 4, carbon atom number be 1 ~ 4 alkynes, monochloro methane, a Celfume, tetrafluoroethene and the vinyl chloride of 1 ~ 4.
The preparation method of a kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention second aspect provides can obtain the uniform negative electrode of lithium ionic secondary battery of component, this lithium rechargeable battery active material is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.The thickness that this negative electrode of lithium ionic secondary battery is applied to when preparing cathode pole piece is not limit.
The third aspect, embodiments provide a kind of cathode pole piece of lithium ion secondary battery, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
Preferably, a is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
Preferably, by mass fraction, carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
Preferably, the particle diameter of silicon alloy kernel is 10 ~ 30 μm.
Preferably, collector is plane Copper Foil or punching Copper Foil.
A kind of cathode pole piece of lithium ion secondary battery that the embodiment of the present invention third aspect provides has excellent cycle performance and efficiency first, and wherein the thickness of negative electrode of lithium ionic secondary battery is not limit.
Fourth aspect, embodiments provide a kind of lithium rechargeable battery, described lithium rechargeable battery is made up of cathode pole piece of lithium ion secondary battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
Preferably, a is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
Preferably, by mass fraction, carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
Preferably, the particle diameter of silicon alloy kernel is 10 ~ 30 μm.
The lithium rechargeable battery energy density that embodiment of the present invention fourth aspect provides is high and cycle performance is good.
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 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 rich lithium solid solution anode composite material 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; under the prerequisite not departing from 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 negative electrode of lithium ionic secondary battery, in order to improve cycle performance and the efficiency first of existing negative active core-shell material.Embodiment of the present invention second aspect provides the preparation method of described negative electrode of lithium ionic secondary battery.The embodiment of the present invention third aspect provides the cathode pole piece of lithium ion secondary battery comprising described negative electrode of lithium ionic secondary battery, and embodiment of the present invention fourth aspect provides the lithium rechargeable battery comprising described negative electrode of lithium ionic secondary battery, this lithium rechargeable battery energy density is high and cycle performance is good.
First aspect, embodiments provide a kind of negative electrode of lithium ionic secondary battery, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
A is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
By mass fraction, carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
The particle diameter of silicon alloy kernel is 10 ~ 30 μm.
A kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention first aspect provides is novel composite material, silicon alloy kernel is wherein polynary negative active core-shell material, Si and Al is basic phase, Sn and transition metal Co, Ni, Ti, Fe, Cu, Mn, Mo, the volumetric expansion that the Si that V and Cr can cushion height ratio capacity to a certain extent occurs when lithium rechargeable battery discharge and recharge, Ge is introduced in the specific capacity and conductivity that improve this negative electrode of lithium ionic secondary battery to a certain extent, the carbon-coating that silicon alloy core surface is coated simultaneously effectively can avoid silicon and electrolyte generation side reaction.This negative electrode of lithium ionic secondary battery has excellent cycle performance and efficiency first.
Second aspect, embodiments provides a kind of preparation method of negative electrode of lithium ionic secondary battery, as shown in Figure 1, comprises the following steps:
(1) get metal Si, Ge, Al and M, according to chemical expression be: Si age bal cm dproportioning is mixed to form mixture, and a, b, c and d represent molar fraction respectively, and a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more;
(2) described mixture is placed in electric arc induction furnace, melting at 800 ~ 1000 DEG C of temperature under vacuum or argon shield condition, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, under vacuum or argon shield condition at 800 ~ 1000 DEG C of temperature secondary smelting, become thin slice or bulk by melt-quenching method preparation, carry out ball milling subsequently and obtain pulverous silicon alloy kernel;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 400 ~ 1000 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and carbon source, argon gas and carbon source total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described carbon source accounts for 10% ~ 30% of argon gas and carbon source cumulative volume, heats up and keeps in-furnace temperature to be 400 ~ 1000 DEG C of reaction 5 ~ 40min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
In the step (2) of the embodiment of the present invention, the temperature of twice melting is 800 ~ 1000 DEG C, in this temperature range, impurity in raw metal such as metal oxide generation deoxygenation can be reduced, to improve the purity of target product, and can ensure that a large amount of evaporations does not occur metallic element, therefore can the chemical composition of goal of regulation and control product comparatively accurately.Preferably, smelting temperature is 900 ~ 950 DEG C.Preferably, under argon gas atmosphere, air pressure is 0.1 ~ 0.2MPa.
" being cast into ingot casting subsequently " in the present invention is conventional cooling and casting, in order to the product completing first time melting is made target shape and size.Have the ingot casting of target shape and size and " become thin slice or bulk by melt-quenching method preparation " subsequently, this process is conventional quick cooling and casting, in order to thin slice or the bulk of crystal structure during obtained maintenance chilling temperature.Described target shape and size are not limit, and its object is only that the product after by pill heat is cast into the ingot casting being convenient to secondary smelting of small volume.
A is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
By mass fraction, carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
The particle diameter of silicon alloy kernel is 10 ~ 30 μm.
The step (3) of the embodiment of the present invention is coated for adopting chemical vapour deposition technique to carry out carbon-coating to silicon alloy kernel, thus the silicon solved in silicon alloy kernel will generate the problem of electrolyte passivating film in electrolyte generation side reaction.
It is one in alkane, the carbon atom number alkene that is 1 ~ 4, carbon atom number be 1 ~ 4 alkynes, monochloro methane, a Celfume, tetrafluoroethene and the vinyl chloride of 1 ~ 4 that described carbon source is selected from carbon atom number.
The preparation method of a kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention second aspect provides can obtain the uniform negative electrode of lithium ionic secondary battery of component, this lithium rechargeable battery active material is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.The thickness that this negative electrode of lithium ionic secondary battery is applied to when preparing cathode pole piece is not limit.
The third aspect, embodiments provide a kind of cathode pole piece of lithium ion secondary battery, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
A is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
By mass fraction, carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
The particle diameter of silicon alloy kernel is 10 ~ 30 μm.
Collector is plane Copper Foil or punching Copper Foil.
A kind of cathode pole piece of lithium ion secondary battery that the embodiment of the present invention third aspect provides has excellent cycle performance and efficiency first, and wherein the thickness of negative electrode of lithium ionic secondary battery is not limit.
Fourth aspect, embodiments provide a kind of lithium rechargeable battery, described lithium rechargeable battery is made up of cathode pole piece of lithium ion secondary battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
A is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
By mass fraction, carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
The particle diameter of silicon alloy kernel is 10 ~ 30 μm.
Lithium rechargeable battery can be flexible packing lithium ion secondary battery, can be also button cell, make all in a conventional manner.
The lithium rechargeable battery energy density that embodiment of the present invention fourth aspect provides is high and cycle performance is good.
Multiple embodiment is divided to be further detailed the embodiment of the present invention below.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 is changed and implements.
Embodiment one
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al and Co, according to chemical expression be: Si 0.65ge 0.05al 0.05co 0.25proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 950 DEG C of temperature under vacuum, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, secondary smelting at 950 DEG C of temperature under vacuum, become thin slice by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous silicon alloy kernel that particle diameter is 25 μm;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 600 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and acetylene, argon gas and acetylene total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described acetylene accounts for 10% of argon gas and acetylene cumulative volume, heats up and keeps in-furnace temperature to be 700 DEG C of reaction 30min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si 0.65ge 0.05al 0.05co 0.25, by mass fraction, described carbon-coating accounts for 4% of described negative electrode of lithium ionic secondary battery quality.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A1.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a1 after punching glove box.
Embodiment two
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al and Fe, according to chemical expression be: Si 0.55ge 0.05al 0.08fe 0.32proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 900 DEG C of temperature under vacuum, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, secondary smelting at 900 DEG C of temperature under vacuum, become thin slice by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous silicon alloy kernel that particle diameter is 10 μm;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 500 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and ethene, argon gas and ethene total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described ethene accounts for 10% of argon gas and ethene cumulative volume, heats up and keeps in-furnace temperature to be 650 DEG C of reaction 5min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si 0.55ge 0.05al 0.08fe 0.32, by mass fraction, described carbon-coating accounts for 1% of described negative electrode of lithium ionic secondary battery quality.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A2.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a2 after punching glove box.
Embodiment three
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al and Ti, according to chemical expression be: Si 0.60ge 0.02al 0.05ti 0.33proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 1000 DEG C of temperature under vacuum, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, secondary smelting at 1000 DEG C of temperature under vacuum, become block by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous silicon alloy kernel that particle diameter is 30 μm;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 700 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and tetrafluoroethene, argon gas and tetrafluoroethene total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described tetrafluoroethene accounts for 30% of argon gas and tetrafluoroethene cumulative volume, heats up and keeps in-furnace temperature to be 1000 DEG C of reaction 30min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si 0.60ge 0.02al 0.05ti 0.33, by mass fraction, described carbon-coating accounts for 10% of described negative electrode of lithium ionic secondary battery quality.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A3.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a3 after punching glove box.
Embodiment four
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al and Ni, according to chemical expression be: Si 0.30ge 0.10al 0.20ni 0.40proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 800 DEG C of temperature under vacuum protection condition, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, secondary smelting at 800 DEG C of temperature under vacuum, become thin slice by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous silicon alloy kernel that particle diameter is 20 μm;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 400 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and methane, argon gas and methane total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described methane accounts for 20% of argon gas and methane cumulative volume, heats up and keeps in-furnace temperature to be 650 DEG C of reaction 40min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si 0.30ge 0.10al 0.20ni 0.40, by mass fraction, described carbon-coating accounts for 6% of described negative electrode of lithium ionic secondary battery quality.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A4.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a4 after punching glove box.
Embodiment five
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al and V, according to chemical expression be: Si 0.20ge 0.04al 0.06v 0.70proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 1000 DEG C of temperature under argon shield condition, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, under argon shield condition at 1000 DEG C of temperature secondary smelting, become block by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous silicon alloy kernel that particle diameter is 30 μm;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 600 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and vinyl chloride, argon gas and vinyl chloride total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described vinyl chloride accounts for 10% of argon gas and vinyl chloride cumulative volume, heats up and keeps in-furnace temperature to be 750 DEG C of reaction 30min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si 0.20ge 0.04al 0.06v 0.70, by mass fraction, described carbon-coating accounts for 6% of described negative electrode of lithium ionic secondary battery quality.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A5.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a5 after punching glove box.
Embodiment six
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al and Mn, according to chemical expression be: Si 0.70ge 0.001al 0.0499mn 0.25proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 1000 DEG C of temperature under argon shield condition, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, under argon shield condition at 1000 DEG C of temperature secondary smelting, become thin slice by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous silicon alloy kernel that particle diameter is 10 μm;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 600 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and acetylene, argon gas and acetylene total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described acetylene accounts for 20% of argon gas and acetylene cumulative volume, heats up and keeps in-furnace temperature to be 700 DEG C of reaction 40min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si 0.70ge 0.001al 0.0499mn 0.25, by mass fraction, described carbon-coating accounts for 8% of described negative electrode of lithium ionic secondary battery quality.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A6.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a6 after punching glove box.
Embodiment seven
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al, Sn and Cu, according to chemical expression be: Si 0.20ge 0.05al 0.50(Sn+Cu) 0.25(the molar fraction ratio of Sn and Cu is 4: 1) proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 800 DEG C of temperature under argon shield condition, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, under argon shield condition at 800 DEG C of temperature secondary smelting, become thin slice by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous silicon alloy kernel that particle diameter is 20 μm;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 600 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and acetylene, argon gas and acetylene total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described acetylene accounts for 10% of argon gas and acetylene cumulative volume, heats up and keeps in-furnace temperature to be 700 DEG C of reaction 30min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si 0.20ge 0.05al 0.50(Sn+Cu) 0.25(the molar fraction ratio of Sn and Cu is 4: 1), by mass fraction, described carbon-coating accounts for 2% of described negative electrode of lithium ionic secondary battery quality.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A7.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a7 after punching glove box.
Embodiment eight
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al, Mo and Cr, according to chemical expression be: Si 0.50ge 0.02al 0.08(Mo+Cr) 0.40(the molar fraction ratio of Mo and Cr is 1: 1) proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 1000 DEG C of temperature under vacuum, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, secondary smelting at 1000 DEG C of temperature under vacuum, become thin slice by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous silicon alloy kernel that particle diameter is 25 μm;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 700 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and tetrafluoroethene, argon gas and tetrafluoroethene total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described tetrafluoroethene accounts for 30% of argon gas and tetrafluoroethene cumulative volume, heats up and keeps in-furnace temperature to be 1000 DEG C of reaction 30min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si 0.50ge 0.02al 0.08(Mo+Cr) 0.40(the molar fraction ratio of Mo and Cr is 1: 1), by mass fraction, described carbon-coating accounts for 9% of described negative electrode of lithium ionic secondary battery quality.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A8.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a8 after punching glove box.
Comparative example one
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Al and Co, according to chemical expression be: Si 60al 10co 30proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 950 DEG C of temperature under vacuum, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, secondary smelting at 950 DEG C of temperature under vacuum, become thin slice by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain pulverous negative electrode of lithium ionic secondary battery that particle diameter is 25 μm.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A9.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a9 after punching glove box.
Comparative example two
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) get metal Si, Ge, Al and Co, according to chemical expression be: Si 30ge 10al 20co 40proportioning is mixed to form mixture;
(2) described mixture is placed in electric arc induction furnace, melting at 950 DEG C of temperature under vacuum, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, secondary smelting at 950 DEG C of temperature under vacuum, become thin slice by melt-quenching method preparation, in absolute ethyl alcohol, carry out ball milling subsequently obtain the negative electrode of lithium ionic secondary battery that particle diameter is 25 μm.
The preparation of cathode pole piece of lithium ion secondary battery
By above-mentioned negative electrode of lithium ionic secondary battery, carbon fiber, Lithium polyacrylate and 1-METHYLPYRROLIDONE according to 100: 2: 2: 200 weight ratio mix, this mixed slurry is uniformly coated on the Copper Foil of 0.008 millimeter, 110 DEG C of oven dry, roll-in obtains cathode pole piece of lithium ion secondary battery.This cathode pole piece of lithium ion secondary battery is cut to size 480mm × 45mm.
The preparation of anode piece of lithium ion secondary battery
Cobalt acid lithium, acetylene black, polytetrafluoroethylene and 1-METHYLPYRROLIDONE are mixed into mixed slurry according to the ratio that weight ratio is 100: 3: 2: 50, this mixed slurry is coated on the aluminium foil of 0.016mm uniformly, then oven dry, roll-in at 110 DEG C, cuts to size 485mm × 44mm.
The preparation of lithium rechargeable battery
Flexible packing lithium ion secondary battery: above-mentioned cathode pole piece of lithium ion secondary battery, anode piece of lithium ion secondary battery and Celgard2400 polypropylene screen are wound into a square lithium ion secondary battery pole piece, then lithium hexafluoro phosphate are dissolved in vinyl carbonate according to the concentration of 1mol/L: dimethyl carbonate is form nonaqueous electrolytic solution in the mixed solvent of 1: 1.This nonaqueous electrolytic solution is injected aluminum plastic film with the amount of 3.8g/Ah, and sealing, makes flexible packing lithium ion secondary battery A10.
Buckle type lithium-ion secondary cell: above-mentioned cathode pole piece of lithium ion secondary battery is assembled into buckle type lithium-ion secondary cell a10 after punching glove box.
Effect example
For providing powerful support for the beneficial effect of the embodiment of the present invention, provide effect example as follows, in order to evaluate and test the performance of the product that the embodiment of the present invention provides.
One, volume test
Buckle type lithium-ion secondary cell a1 to a10 obtained in embodiment one ~ embodiment eight and comparative example is placed on discharge and recharge cashier's office in a shop respectively, record with 0.2C constant-current discharge to capacity that 0.01V obtains (being designated as C), shelve 10 minutes, record is with 0.2C constant current charge to 2V capacity (being designated as D), and the D obtained is material capacity.Be calculated as efficiency first according to D/C × 100%, outcome record in Table 1.
The specific capacity of table 1. buckle type lithium-ion secondary cell a1 to a10 and first efficiency
Battery Specific capacity (mAh/g) Efficiency (%) first
a1 1287 80.1
a2 1163 83.2
a3 1047 78.9
a4 998 92.5
a5 432 88.7
a6 1243 89.4
a7 489 87.6
a8 931 78.4
a9 1013 51.9
a10 1031 60.8
As can be seen from Table 1, compare ratio, the negative electrode of lithium ionic secondary battery that embodiment one ~ embodiment eight obtains has higher specific capacity and higher efficiency first.
Two, normal temperature and high temperature cyclic performance test
Flexible packing lithium ion secondary battery A1 to A10 obtained in embodiment one ~ embodiment eight and comparative example is placed on charge-discharge test cashier's office in a shop respectively, first carry out constant-current constant-voltage charging to upper voltage limit 3.8V with 1C, after shelving 10 minutes, 2.5V is discharged to from 3.8V with the electric current of 1C, record initial discharge capacity, then after repeating above-mentioned steps 300 times, the discharge capacity after record circulation 300 times.According to formulae discovery 300 circulation volume sustainment rates of capacity dimension holdup=(the 300th discharge capacity/initial discharge capacity) × 100%.
Above-mentioned experiment is tested respectively under normal temperature 25 DEG C and high temperature 60 DEG C of environment, and outcome record in table 2.
Table 2. flexible packing lithium ion secondary battery A1 to A10 is 300 circulation volume sustainment rates at ambient and elevated temperatures
As can be seen from Table 2, compare ratio, the negative electrode of lithium ionic secondary battery that embodiment one ~ embodiment eight obtains has good normal-temperature circulating performance and good high temperature cyclic performance.
Three, high-temperature storage performance test
Flexible packing lithium ion secondary battery A1 to A10 obtained in embodiment one ~ embodiment eight and comparative example is placed on charge-discharge test cashier's office in a shop respectively, first carry out constant-current constant-voltage charging to upper voltage limit 3.8V with 1C, after shelving 10 minutes, 2.5V is discharged to from 3.8V, record initial capacity (discharge capacity) with the electric current of 1C.Then be placed in 60 DEG C of high temperature ovens storages after 7 days, be discharged to 2.5V with the electric current of 1C from 3.8V, record storage volume (discharge capacity).Discharge and recharge 3 times as stated above, records last discharge capacity, is recovery capacity again.Hold facility by measure=electric discharge storage volume/electric discharge initial capacity, the formulae discovery of capacity restorability=electric discharge recovery capacity/electric discharge initial capacity, outcome record in table 3.
Table 3. flexible packing lithium ion secondary battery A1 to A10 is in high temperature storage capacity hold facility and recovery capability
Battery High-temperature storage capacity hold facility (%) High-temperature storage capacity restorability (%)
A1 83.2 84.1
A2 82.5 83.7
A3 84.4 84.9
A4 87.9 89.1
A5 78.3 79.4
A6 87.3 88.8
A7 80.4 81.5
A8 83.6 84.8
A9 70.3 71.9
A10 72.5 74.4
As can be seen from Table 3, compare ratio, the negative electrode of lithium ionic secondary battery that embodiment one ~ embodiment eight obtains has higher capability retention.

Claims (10)

1. a negative electrode of lithium ionic secondary battery, is characterized in that, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
2. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, is characterized in that, described a is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
3. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, is characterized in that, by mass fraction, described carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
4. a preparation method for negative electrode of lithium ionic secondary battery, is characterized in that, comprises the following steps:
(1) get metal Si, Ge, Al and M, according to chemical expression be: Si age bal cm dproportioning is mixed to form mixture, and a, b, c and d represent molar fraction respectively, and a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more;
(2) described mixture is placed in electric arc induction furnace, melting at 800 ~ 1000 DEG C of temperature under vacuum or argon shield condition, be cast into ingot casting subsequently, then described ingot casting is placed in fast melt-quenching stove, under vacuum or argon shield condition at 800 ~ 1000 DEG C of temperature secondary smelting, become thin slice or bulk by melt-quenching method preparation, carry out ball milling subsequently and obtain pulverous silicon alloy kernel;
(3) described silicon alloy kernel is placed in tube furnace ceramic boat, under vacuum, in-furnace temperature is warming up to 400 ~ 1000 DEG C with the speed of 10 DEG C/min, then passes into protective gas argon gas and carbon source, argon gas and carbon source total volumetric flow rate are 1Nm 3/ h, by volume mark meter, described carbon source accounts for 10% ~ 30% of argon gas and carbon source cumulative volume, heats up and keeps in-furnace temperature to be 400 ~ 1000 DEG C of reaction 5 ~ 40min, stopping subsequently heating and being cooled to room temperature, obtained negative electrode of lithium ionic secondary battery.
5. the preparation method of a kind of negative electrode of lithium ionic secondary battery as claimed in claim 4, is characterized in that, described a is 30% ~ 50%, b be 2% ~ 10%, c be 5% ~ 25%, d is 40% ~ 50%.
6. the preparation method of a kind of negative electrode of lithium ionic secondary battery as claimed in claim 4, it is characterized in that, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, by mass fraction, described carbon-coating accounts for 2% ~ 8% of negative electrode of lithium ionic secondary battery quality.
7. the preparation method of a kind of negative electrode of lithium ionic secondary battery as claimed in claim 4, is characterized in that, described smelting temperature is 900 ~ 950 DEG C.
8. the preparation method of a kind of negative electrode of lithium ionic secondary battery as claimed in claim 4, it is characterized in that, it is one in alkane, the carbon atom number alkene that is 1 ~ 4, carbon atom number be 1 ~ 4 alkynes, monochloro methane, a Celfume, tetrafluoroethene and the vinyl chloride of 1 ~ 4 that described carbon source is selected from carbon atom number.
9. a cathode pole piece of lithium ion secondary battery, it is characterized in that, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
10. a lithium rechargeable battery, it is characterized in that, described lithium rechargeable battery is made up of cathode pole piece of lithium ion secondary battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery is the core-shell structure copolymer clad structure that carbon-coating is coated on the formation of silicon alloy core surface, and the chemical expression of described silicon alloy kernel is: Si age bal cm da, b, c and d represent molar fraction respectively, a is 20% ~ 70%, b is 0.01% ~ 10%, c to be 1% ~ 50%, d be 25% ~ 75%, M is selected from Sn, Co, Ni, Ti, Fe, Cu, Mn, Mo, V and Cr one or more, by mass fraction, described carbon-coating accounts for 1% ~ 10% of described negative electrode of lithium ionic secondary battery quality.
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