CN106505190B - A kind of three-dimensional dendritic silicon negative electrode material and preparation method - Google Patents

A kind of three-dimensional dendritic silicon negative electrode material and preparation method Download PDF

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CN106505190B
CN106505190B CN201610904123.7A CN201610904123A CN106505190B CN 106505190 B CN106505190 B CN 106505190B CN 201610904123 A CN201610904123 A CN 201610904123A CN 106505190 B CN106505190 B CN 106505190B
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silicon particle
silicon
preparation
electrode material
dimensional dendritic
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CN106505190A (en
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陈庆
陈兵
王镭迪
曾军堂
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Wuzhou Tongxin Energy Materials Co ltd
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Huizhou De Long Long Energy Technology 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

The present invention relates to silicium cathode electrode material technical fields, disclose a kind of three-dimensional dendritic silicon negative electrode material and preparation method, wherein the silicon particle of nanosizing is the subparticle of mouth of splitting one by one, silicon materials volume change only occurs in inside single nanoparticle during lithium ion disengaging, and volume change is buffered by underbead crack and offset.And apparent volume expansion is not entirely occurred by electrode slice prepared by silicon materials.Silicon materials are efficiently solved as lithium cell cathode material, the volume occurred during lithium deintercalation acutely expands, preparation method is after dispersing nanometer silicon particle by dispersing agent, suddenly freeze through liquid nitrogen, then through microwave fast heating, a nanometer silicon particle is burst, the silicon particle of three-dimensional dendritic crackle is formed.

Description

A kind of three-dimensional dendritic silicon negative electrode material and preparation method
Technical field
The present invention relates to silicium cathode electrode material technical field, specifically a kind of three-dimensional dendritic silicon negative electrode material and system Preparation Method.
Background technique
Silicon materials are considered very likely substitution graphite material due to the advantages that its theoretical capacity is big, and preparation cost is cheap Expect the substance as next-generation lithium battery negative electrode material.Especially have become lithium battery industry development in current battery capacity Bottleneck, silicium cathode material attracts attention with large capacity.The technical issues of it is mainly faced is during lithium ion passes in and out Violent expansion occurs for silicon materials volume, to rupture dusting, generates the consequence of material dusting.
Have at present by silicon and metal alloy, nonmetallic compound compound reduction charge and discharge process in volume expansion to Material electrochemical performance bring influences, such as improves its chemical property by the variation, doping and carbon coating of appearance structure. However, since cubical expansivity is up to 400% in charge and discharge for silicon, either by the cladding of mixing, surface carbon with carbon, also Be it is compound by the way that conducting polymer, metal alloy is added, not can solve the expansion of such large volume.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defects of the prior art, provide a kind of three-dimensional dendritic silicon negative electrode Material and preparation method.
In order to solve the above technical problems, the present invention the following technical schemes are provided:
A kind of three-dimensional dendritic silicon negative electrode material, including silicon particle, the silicon particle are the silicon particle of nanosizing, silicon Particle has three-dimensional dendritic crackle, and the inside and surface of silicon particle are in three-dimensional dendritic crackle, similar to the mouth that splits one by one Subparticle.
A kind of preparation method of three-dimensional dendritic silicon negative electrode material, the specific steps of which are as follows:
It is impregnated 48 hours 1. the silicon particle of nanosizing is immersed in enough intercalators, activates silicon particle, it is micro- to take out silicon Grain centrifugal drying, obtains intercalation silicon particle；Wherein intercalator pH is 7.7-8；
Disperse 2. the intercalation silicon particle of step 1. is added in the excess chlorine salt dissolving of melting;
3. 2. molten mixture that step is obtained suddenly freezes through liquid nitrogen, obtains low-temperature mixed object；
4. 3. low-temperature mixed object that step is obtained bursts a nanometer silicon particle, then clearly through microwave fast heating Filter is washed, the silicon particle that product is three-dimensional dendritic crackle is obtained.
Preferably, the intercalator be mass ratio be 3:4:1 dimethyl sulfone, formamide, polyethylene glycol mixture.
Preferably, the chlorate of the melting is the sodium chloride and magnesium chloride molten mixture that mass ratio is 1:1.
Compared with the prior art, the invention has the beneficial effects that: the invention discloses a kind of three-dimensional dendritic silicon negative electricities Pole material and preparation method, wherein the silicon particle of nanosizing is the subparticle of mouth of splitting one by one, passes in and out process in lithium ion Middle silicon materials volume change only occurs in inside single nanoparticle, and volume change is buffered by underbead crack and offset.And it is whole Apparent volume expansion does not occur for a electrode slice by silicon materials preparation.Silicon materials are efficiently solved as lithium ion battery anode material Material, the volume occurred during lithium deintercalation acutely expand, and preparation method is by nanometer silicon particle by intercalation activation, and with It is compound to melt chlorate, suddenly freezes through liquid nitrogen, then through microwave fast heating, bursts a nanometer silicon particle, form three-dimensional branch The silicon particle of shape crackle.
Detailed description of the invention
Fig. 1 is structure of the invention display figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
A kind of three-dimensional dendritic silicon negative electrode material as shown in Figure 1, including silicon particle, the silicon particle are nanosizing Silicon particle, silicon particle has three-dimensional dendritic crackle, and the inside and surface of silicon particle are similar to one in three-dimensional dendritic crackle Each and every one split the subparticle of mouth.
Embodiment 1
A kind of preparation method of three-dimensional dendritic silicon negative electrode material, the specific steps of which are as follows:
It is impregnated 1. being immersed in the silicon particle of nanosizing in the intercalator being made of dimethyl sulfone, formamide, polyethylene glycol 48 hours, silicon particle is activated, take out silicon particle centrifugal drying, obtains intercalation silicon particle；Wherein intercalator pH is 7.7-8；
Disperse 2. the intercalation silicon particle of step 1. is added in the excess chlorination sodium of melting;
3. 2. molten mixture that step is obtained suddenly freezes through liquid nitrogen, obtains low-temperature mixed object；
4. 3. low-temperature mixed object that step is obtained bursts a nanometer silicon particle, then clearly through microwave fast heating Filter is washed, the silicon particle that product is three-dimensional dendritic crackle is obtained.
Embodiment 2
A kind of preparation method of three-dimensional dendritic silicon negative electrode material, the specific steps of which are as follows:
It impregnates 48 hours, makes 1. the silicon particle of nanosizing is immersed in the intercalator being made of dimethyl sulfone, formamide Silicon particle activation, takes out silicon particle centrifugal drying, obtains intercalation silicon particle；Wherein intercalator pH is 7.7-8；
2. the intercalation silicon particle of step 1. to be added to the excessive melting mixing being made of sodium chloride and magnesium chloride of melting Disperse in object;
3. 2. molten mixture that step is obtained suddenly freezes through liquid nitrogen, obtains low-temperature mixed object；
4. 3. low-temperature mixed object that step is obtained bursts a nanometer silicon particle, then clearly through microwave fast heating Filter is washed, the silicon particle that product is three-dimensional dendritic crackle is obtained.
Embodiment 3
A kind of preparation method of three-dimensional dendritic silicon negative electrode material, the specific steps of which are as follows:
It is impregnated 48 hours 1. the silicon particle of nanosizing is immersed in enough intercalators, activates silicon particle, it is micro- to take out silicon Grain centrifugal drying, obtains intercalation silicon particle；Wherein intercalator pH is 7.7-8；
Disperse 2. the intercalation silicon particle of step 1. is added in the excess chlorine salt dissolving of melting;
3. 2. molten mixture that step is obtained suddenly freezes through liquid nitrogen, obtains low-temperature mixed object；
4. 3. low-temperature mixed object that step is obtained bursts a nanometer silicon particle, then clearly through microwave fast heating Filter is washed, the silicon particle that product is three-dimensional dendritic crackle is obtained.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (3)

1. a kind of preparation method of three-dimensional dendritic silicon negative electrode material, it is characterised in that: the specific steps of which are as follows:
Impregnated 48 hours 1. the silicon particle of nanosizing is immersed in enough intercalators, activate silicon particle, take out silicon particle from The heart is dry, obtains intercalation silicon particle；Wherein intercalator pH is 7.7-8；
Disperse 2. the intercalation silicon particle of step 1. is added in the excess chlorine salt dissolving of melting;
3. 2. molten mixture that step is obtained suddenly freezes through liquid nitrogen, obtains low-temperature mixed object；
4. 3. low-temperature mixed object that step is obtained bursts a nanometer silicon particle, then cleaned through microwave fast heating Filter obtains the silicon particle that product is three-dimensional dendritic crackle.
2. a kind of preparation method of three-dimensional dendritic silicon negative electrode material according to claim 1, it is characterised in that: described Intercalator be mass ratio be 3:4:1 dimethyl sulfone, formamide, polyethylene glycol mixture.
3. a kind of preparation method of three-dimensional dendritic silicon negative electrode material according to claim 1, it is characterised in that: described The chlorate of melting is the sodium chloride and magnesium chloride molten mixture that mass ratio is 1:1.
CN201610904123.7A 2016-10-18 2016-10-18 A kind of three-dimensional dendritic silicon negative electrode material and preparation method Active CN106505190B (en)

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CN112614982A (en) * 2020-12-21 2021-04-06 惠州锂威新能源科技有限公司 Preparation method of silicon-oxygen negative electrode material of lithium ion battery, negative electrode material and lithium ion battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010032159A1 (en) * 2008-09-17 2010-03-25 Nxp B.V. 2d or 3d electrochemical device employing composit active electrodes
WO2011041468A1 (en) * 2009-09-29 2011-04-07 Georgia Tech Research Corporation Electrodes, lithium-ion batteries, and methods of making and using same
CN104876213A (en) * 2015-05-04 2015-09-02 北京化工大学 Graphene material and preparation method of electrode material of graphene material
CN104900486A (en) * 2015-04-23 2015-09-09 西北工业大学 Preparation method of multilevel dentritic silicon nanowire
CN105024045A (en) * 2014-04-22 2015-11-04 微宏动力***（湖州）有限公司 Preparation method of nano silicon for lithium battery cathode material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010032159A1 (en) * 2008-09-17 2010-03-25 Nxp B.V. 2d or 3d electrochemical device employing composit active electrodes
WO2011041468A1 (en) * 2009-09-29 2011-04-07 Georgia Tech Research Corporation Electrodes, lithium-ion batteries, and methods of making and using same
CN105024045A (en) * 2014-04-22 2015-11-04 微宏动力***（湖州）有限公司 Preparation method of nano silicon for lithium battery cathode material
CN104900486A (en) * 2015-04-23 2015-09-09 西北工业大学 Preparation method of multilevel dentritic silicon nanowire
CN104876213A (en) * 2015-05-04 2015-09-02 北京化工大学 Graphene material and preparation method of electrode material of graphene material

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