CN110137479A - A kind of lithium ion battery anode active material method of modifying - Google Patents

A kind of lithium ion battery anode active material method of modifying Download PDF

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Publication number
CN110137479A
CN110137479A CN201910490949.7A CN201910490949A CN110137479A CN 110137479 A CN110137479 A CN 110137479A CN 201910490949 A CN201910490949 A CN 201910490949A CN 110137479 A CN110137479 A CN 110137479A
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CN
China
Prior art keywords
sio
lithium ion
ion battery
active material
modifying
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Pending
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CN201910490949.7A
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Chinese (zh)
Inventor
何丹农
焦靖华
张芳
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Priority to CN201910490949.7A priority Critical patent/CN110137479A/en
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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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses a kind of lithium ion battery anode active material method of modifying, and a certain amount of polyvinyl alcohol (PVA) is dissolved in 90 DEG C or more of hot water；A certain amount of SiO is addedxPowder, being sufficiently stirred makes SiOxIt is uniformly dispersed to obtain SiOxSuspension；Evaporating water is simultaneously stirred continuously, and obtains gel presoma；This presoma, which is roasted, in argon gas high temperature obtains SiOx/ C composite.Since polyvinyl alcohol (PVA) is water-soluble high-molecular material, it can avoid using toxic organic solvent dispersion when as carbon source packet carbon, be good for the environment.By the SiO before and after packet carbonxSample assembly is significantly improved at battery, corresponding capacity retention ratio, and cycle performance is improved.

Description

A kind of lithium ion battery anode active material method of modifying
Technical field
The invention belongs to field of electrochemical batteries, are related to a kind of negative electrode active material method of modifying of lithium ion battery.
Background technique
Scale energy storage, electric tool, electric car, portable electronic device etc. are to the specific energy of lithium ion battery, ratio Power, safety and cycle life etc. propose increasingly higher demands.Although the performance of lithium ion battery by positive and negative pole material, The influence of many factors such as electrolyte, binder and collector, diaphragm, but the key for influencing its chemical property is to form electricity The electrolyte in pond and the performance of positive and negative pole material, negative electrode material are the key that influence one of lithium ion battery chemical property.
In recent years, SiOxAlso start to show its advantage being used in lithium ion battery Si base negative electrode material, introduce oxygen, So that embedding lithium generates inert component for the first time, this also results in the reduction of absolute volume under removal lithium embedded behavior.It is compared to simple substance Silicon, SiOxMore there are practical potentiality, the lithium ion battery material prospect of great high-energy-density.
In order to improve the chemical property of lithium ion battery negative material, oneself is modified to it as Recent study Emphasis.So far, in order to improve the chemical property of negative electrode material, two major classes technical solution: a kind of approach is with other ions It is bulk phase-doped to material progress, by the structure of stabilizing material, the lattice transformation of material in cyclic process is inhibited to improve material Performance；Another way is exactly to carry out surface to negative electrode material with carbon material, oxide material etc. to be modified.So-called surface is modified New processing is exactly carried out to powder granule surface, powder surface characteristic is made to have biggish change, and it is new to assign powder granule particle Function: can improve dispersibility, the thermal stability of powder particle, improve powder surface activity, make particle have new physics, Chemistry and mechanical performance etc..
Summary of the invention
In view of the deficiencies of the prior art, it is an object of that present invention to provide a kind of modifications of lithium ion battery anode active material Method, with polyvinyl alcohol (PVA) for carbon source, to SiOxMaterial surface coats carbon material, further increases silicon based anode material Circulation volume conservation rate, improve its cycle performance.
In order to solve the above technical problems, the present invention provides a kind of lithium ion battery anode active material method of modifying, the party Method includes step in detail below:
Step 1, a certain amount of polyvinyl alcohol (PVA) is dissolved in 90 DEG C or more of hot water；
Step 2, a certain amount of SiO is addedxPowder, wherein PVA and SiOxMass ratio be 20 ~ 200:100, being sufficiently stirred makes SiOxIt is uniformly dispersed to obtain SiOxSuspension；
Step 3, it evaporating water and is stirred continuously, obtains gel presoma；
Step 4, this presoma is roasted in argon gas high temperature obtain SiOx/ C composite.
Above-mentioned lithium ion battery anode active material method of modifying, wherein roasting forerunner's temperature is 500 ~ 800 DEG C.
Above-mentioned lithium ion battery anode active material method of modifying, wherein a length of 1 ~ 8h when roasting presoma.
The invention has the advantages that polyvinyl alcohol (PVA) is water-soluble high-molecular material, can avoid use when as carbon source packet carbon has The organic solvent dispersion of poison, is good for the environment.By the SiO before and after packet carbonxFor sample assembly at battery, corresponding capacity retention ratio is aobvious It writes and improves, cycle performance is improved.
It is of the invention to be advantageous in that: since polyvinyl alcohol (PVA) is water-soluble high-molecular material, when as carbon source packet carbon It can avoid using toxic organic solvent dispersion, be good for the environment；By the SiO before and after packet carbonxSample assembly is at battery, accordingly Capacity retention ratio significantly improves, and cycle performance is improved.
Detailed description of the invention
The implementation process flow chart of 1 invention of attached drawing.
Specific embodiment
Embodiment 1
A kind of lithium ion battery anode active material method of modifying, flow graph is as shown in Figure 1, according to the following steps:
1,20g polyvinyl alcohol (PVA) is dissolved in 95 DEG C of hot water of 300g；
2, the SiO of 20g is added in above-mentioned PVA solutionxPowder, lasting stirring make SiOxIt is uniformly dispersed to obtain SiOxSuspension；
3, it evaporating water and is stirred continuously on electric furnace, obtains gel presoma；
4, this presoma 6h is roasted in 700 DEG C of argon gas, obtains SiOx/ C composite.
Electrochemical property test:
With SiOx/ C composite is negative electrode material, with conductive carbon black (Super P), sodium carboxymethylcellulose (CMC), butylbenzene rubber Glue (SBR) 80:8:4:8 in mass ratio mixing, using deionized water as solvent, mixing is uniformly coated on collector Cu foil after being slurried On, it is punched into diameter 14mm disk, is then dried 24 hours in 80 DEG C of vacuum oven and obtains SiOx/ C composite electricity Pole piece.
It is to electrode, above-mentioned SiO with metal lithium sheetx/ C composite pole piece be Electrode, Celgard 2035 be every Film, 1.5mol/L lithium hexafluoro phosphate (LiPF6)/ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) is that electrolyte is assembled into CR2016 button cell.Battery is close with the electric current of 80mA/g active material first Degree carries out-charging cycle of discharging, and voltage range is 0.01 ~ 1.5V, and initial charge specific capacity reaches 832mAh/g, recycles 50 ratios Capacity reaches 574mAh/g.
Embodiment 2
A kind of lithium ion battery anode active material method of modifying, according to the following steps:
1,10g polyvinyl alcohol (PVA) is dissolved in 95 DEG C of hot water of 300g；
2, the SiO of 20g is added in above-mentioned PVA solutionxPowder, lasting stirring make SiOxIt is uniformly dispersed to obtain SiOxSuspension；
2, it evaporating water and is stirred continuously on electric furnace, obtains gel presoma；
4, this presoma 5h is roasted in 800 DEG C of argon gas, obtains SiOx/ C composite.
Electrochemical property test:
With SiOx/ C composite is negative electrode material, with conductive carbon black (Super P), sodium carboxymethylcellulose (CMC), butylbenzene rubber Glue (SBR) 80:8:4:8 in mass ratio mixing, using deionized water as solvent, mixing is uniformly coated on collector Cu foil after being slurried On, it is punched into diameter 14mm disk, is then dried 24 hours in 80 DEG C of vacuum oven and obtains SiOx/ C composite electricity Pole piece.
It is to electrode, above-mentioned SiO with metal lithium sheetx/ C composite pole piece be Electrode, Celgard 2035 be every Film, 1.5mol/L lithium hexafluoro phosphate (LiPF6)/ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) is that electrolyte is assembled into CR2016 button cell.Battery is close with the electric current of 80mA/g active material first Degree carries out-charging cycle of discharging, and voltage range is 0.01 ~ 1.5V, and initial charge specific capacity reaches 962mAh/g, recycles 50 ratios Capacity reaches 501mAh/g.
Comparative example 1
With SiOxFor negative electrode material, with conductive carbon black (Super P), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) is pressed Mass ratio 80:8:4:8 mixing, using deionized water as solvent, mixing is uniformly coated on collector Cu foil after being slurried, and is punched into straight Then diameter 14mm disk dries 24 hours in 80 DEG C of vacuum oven and obtains SiOxElectrode slice.
It is to electrode, above-mentioned SiO with metal lithium sheetxPole piece is Electrode, and Celgard 2035 is diaphragm, 1.5mol/L Lithium hexafluoro phosphate (LiPF6)/ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC) (volume ratio 1:1: 1) CR2016 button cell is assembled into for electrolyte.Battery discharge-fill with the current density of 80mA/g active material first Electricity circulation, voltage range are 0.01 ~ 1.5V, and initial charge capacity reaches 1230mAh/g, and recycling 20 capacity is only 453mAh/ g。
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.

Claims (3)

1. a kind of lithium ion battery anode active material method of modifying, which is characterized in that with polyvinyl alcohol (PVA) for carbon source, To SiOxMaterial surface coats carbon material, includes step in detail below:
Step 1, a certain amount of polyvinyl alcohol (PVA) is dissolved in 90 DEG C or more of hot water；
Step 2, a certain amount of SiO is addedxPowder, PVA and SiOxMass ratio be 20 ~ 200:100, being sufficiently stirred makes SiOxPoint It dissipates and uniformly obtains SiOxSuspension；
Step 3, it evaporating water and is stirred continuously, obtains gel presoma；
Step 4, this presoma is roasted in argon gas high temperature obtain SiOx/ C composite.
2. lithium ion battery anode active material method of modifying as described in claim 1, which is characterized in that roasting forerunner's body temperature Degree is 500 ~ 800 DEG C.
3. lithium ion battery anode active material method of modifying as claimed in claim 1 or 2, which is characterized in that presoma roasting The burning time is 1 ~ 8h.
CN201910490949.7A 2019-06-06 2019-06-06 A kind of lithium ion battery anode active material method of modifying Pending CN110137479A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113764626A (en) * 2021-08-17 2021-12-07 上海纳米技术及应用国家工程研究中心有限公司 Modification method of silicon-oxygen negative electrode material of lithium ion battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113764626A (en) * 2021-08-17 2021-12-07 上海纳米技术及应用国家工程研究中心有限公司 Modification method of silicon-oxygen negative electrode material of lithium ion battery

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