CN108963238A - A kind of preparation method of lithium ion cell nano silicon monoxide composite cathode material - Google Patents

A kind of preparation method of lithium ion cell nano silicon monoxide composite cathode material Download PDF

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Publication number
CN108963238A
CN108963238A CN201810911414.8A CN201810911414A CN108963238A CN 108963238 A CN108963238 A CN 108963238A CN 201810911414 A CN201810911414 A CN 201810911414A CN 108963238 A CN108963238 A CN 108963238A
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silicon
preparation
lithium ion
cathode material
nano
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CN201810911414.8A
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叶飞
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Suzhou Na Zhi Hang Amperex Technology Ltd
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Suzhou Na Zhi Hang Amperex Technology 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
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 invention discloses a kind of preparation methods of lithium ion cell nano silicon monoxide composite cathode material.Nano oxidized sub- silicon composite cathode material is prepared by vapour deposition process and staged temperature-raising method, capacity, the sub- silicon of oxidation, which can be greatly improved, in silica-base material has smaller volume expansion with respect to pure silicon, available high performance composite graphite negative electrode capacity is higher than the level of current graphite cathode material, and first charge discharge efficiency, cycle performance, security performance, stability and reliability etc. are obviously improved.

Description

A kind of preparation method of lithium ion cell nano silicon monoxide composite cathode material
Technical field
The present invention relates to a kind of preparation methods of lithium ion cell nano silicon monoxide composite cathode material, belong to new energy Field of material technology is related to a kind of composite negative pole material preparation method more particularly to a kind of preparation of high capacity composite negative pole material The technical field of method.
Background technique
Lithium ion battery because its voltage is high, energy density is high, have extended cycle life, environmental pollution is small the advantages that gain great popularity. As environmentally protective secondary stored energy source, lithium ion battery has the advantages such as light, mobile, high-energy, environmentally protective.But with The fast development of electronic information technology, communication base station, audio-visual equipment, industrial instrumentation, medical instrument, mobile phone, laptop, Electric tool, electric bicycle or even electric car are continuously increased lithium battery demand, close to the energy of lithium ion battery Higher requirements are also raised for the comprehensive performances such as degree, cycle-index, security performance, production cost.Produce it is best in quality, adapt to pair The lithium ion battery material on road is the inevitable choice of each manufacturer.Therefore either improve efficiency of energy utilization, reduce can not Regenerated resources consumption still taps a new source of energy, all inseparable with the innovation and development of material industry.Lithium cell cathode material is in One of the most crucial link in lithium battery industry middle reaches is distributed by battery cost, lithium cell cathode material and other accounting lithiums from 28% or so of sub- battery totle drilling cost.Negative electrode material is as crucial one of the material in current lithium ion battery, its development Most merit attention.
Lithium ion battery is the ideal source of portable electronic device, electric car and energy-storage system, exploitation specific energy height, Safety is good and low-cost new electrode materials are the core contents in Study on Li-ion batteries field, realizes the pass of target Key technology first is that negative electrode material is changed into silica-base material from graphite.
Mature lithium ion battery negative material is mainly graphite type material at present, and theoretical specific capacity is only 372mAh/ G, development potentiality is limited, is unable to satisfy demand of the following lithium ion battery to high-energy density.Sub- silicon materials are aoxidized with higher Theoretical specific capacity (> 2000mAh/g), lower storage lithium response voltage platform, and preparation cost is cheap, therefore become substitution stone A kind of negative electrode material of the great potential of ink.But the electric conductivity for aoxidizing sub- silicon is poor, and property leads to its electrochemistry close to insulator The dynamic performance of reaction is poor.And it aoxidizes the SiO2 for including in sub- silicon materials and is transformed into embedding lithium reaction for the first time The objects phase such as Li4SiO4, Li2Si2O5, consumes more lithium ion, causes first charge-discharge efficiency lower (< 70%).Therefore, it grinds The oxidation Asia silicium cathode material for sending out high conductivity, high first charge-discharge efficiency and good cycling stability a kind of is lithium ion battery neck The technical problem in domain.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of lithium ion cell nano silicon monoxide composite cathode materials Preparation method.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of preparation method of lithium ion cell nano silicon monoxide composite cathode material, feature include the following steps:
(1) gaseous organic carbon source is used, by the method for chemical vapor deposition, is mixed with nano-silicon and nano oxidized sub- silicon, Then ball milling obtains nanoscale carbonization composite material
(2) composite material is poured into deionized water and is stirred evenly, obtain suspension.Resulting suspension is poured into sand mill It is sanded, is then spray-dried, remove moisture removal, obtain dry mixture；
(3) under inert gas protection by mixture obtained in step (2), by staged temperature reaction, Compound Negative is obtained Pole material.It is then placed in planetary ball mill and is crushed, obtain lithium ion cell nano silicon monoxide composite cathode material.
The partial size of nano-silicon is 10-30nm, and the partial size for aoxidizing sub- silicon is 20-50nm.
The revolving speed of ball milling is 500 revs/min in step 1, and the time is for 24 hours.
Staged temperature reaction specifically: be first warming up to 120-150 DEG C, isothermal reaction 3h under nitrogen protection, then heat up To 1000-1200 DEG C, isothermal reaction 12-24h.Heating rate is 10-100 DEG C/min.
The revolving speed of ball mill is 300r/min in step 3.
Advantageous effects of the invention:
Method of the invention is anti-by mixing organic carbon source, nano-silicon and nano oxidized sub- silicon and passing through the heating of ball milling staged It answers, the composite negative pole material of high capacity is prepared, capacity can be greatly improved in silica-base material, the sub- silicon of oxidation has more with respect to pure silicon Small volume expansion, available high performance composite graphite negative electrode capacity are higher than the level of current graphite cathode material, for the first time Efficiency, cycle performance, security performance, stability and reliability etc. are obviously improved, and product can be widely used for new energy The fields such as automobile, digital electric and energy storage.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo of composite negative pole material prepared by the embodiment of the present invention 1.
Specific embodiment
The invention will be further described combined with specific embodiments below.Following embodiment is only used for clearly illustrating Technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
It is mixed with nano-silicon and nano oxidized sub- silicon, then using gaseous organic carbon source by the method for chemical vapor deposition Ball milling for 24 hours, obtains nanoscale carbonization composite material under 500r/min revolving speed.Composite material is poured into deionized water and is stirred It is even, obtain suspension.Resulting suspension is poured into sand mill and is sanded, is then spray-dried, moisture removal is removed, is obtained To dry mixture；By resulting mixture: being first warming up to 120 DEG C, isothermal reaction 3h under nitrogen protection, then be warming up to 1000 DEG C, isothermal reaction 12h.Heating rate is 100 DEG C/min.Obtain composite negative pole material.It is then placed in planetary type ball-milling It is crushed in machine, obtains lithium ion cell nano silicon monoxide composite cathode material.
Embodiment 2
It is mixed with nano-silicon and nano oxidized sub- silicon, then using gaseous organic carbon source by the method for chemical vapor deposition Ball milling for 24 hours, obtains nanoscale carbonization composite material under 500r/min revolving speed.Composite material is poured into deionized water and is stirred It is even, obtain suspension.Resulting suspension is poured into sand mill and is sanded, is then spray-dried, moisture removal is removed, is obtained To dry mixture；By resulting mixture: being first warming up to 150 DEG C, isothermal reaction 3h under nitrogen protection, then be warming up to 1200 DEG C, isothermal reaction is for 24 hours.Heating rate is 10 DEG C/min.Obtain composite negative pole material.It is then placed in planetary ball mill In be crushed, obtain lithium ion cell nano silicon monoxide composite cathode material.
Embodiment 3
It is mixed with nano-silicon and nano oxidized sub- silicon, then using gaseous organic carbon source by the method for chemical vapor deposition Ball milling for 24 hours, obtains nanoscale carbonization composite material under 500r/min revolving speed.Composite material is poured into deionized water and is stirred It is even, obtain suspension.Resulting suspension is poured into sand mill and is sanded, is then spray-dried, moisture removal is removed, is obtained To dry mixture；By resulting mixture: being first warming up to 140 DEG C, isothermal reaction 3h under nitrogen protection, then be warming up to 1500 DEG C, isothermal reaction 18h.Heating rate is 50 DEG C/min.Obtain composite negative pole material.It is then placed in planetary ball mill In be crushed, obtain lithium ion cell nano silicon monoxide composite cathode material.
Embodiment 4
It is mixed with nano-silicon and nano oxidized sub- silicon, then using gaseous organic carbon source by the method for chemical vapor deposition Ball milling for 24 hours, obtains nanoscale carbonization composite material under 500r/min revolving speed.Composite material is poured into deionized water and is stirred It is even, obtain suspension.Resulting suspension is poured into sand mill and is sanded, is then spray-dried, moisture removal is removed, is obtained To dry mixture；By resulting mixture: being first warming up to 130 DEG C, isothermal reaction 3h under nitrogen protection, then be warming up to 1000 DEG C, isothermal reaction 16h.Heating rate is 80 DEG C/min.Obtain composite negative pole material.It is then placed in planetary ball mill In be crushed, obtain lithium ion cell nano silicon monoxide composite cathode material.
Battery testing is carried out using conventional method, which is 965.9-1030.5 mAh/ G, initial charge specific capacity are 689.5-723.8 mAh/g, and coulombic efficiency is 65.6-70.9% for the first time, and second week coulombic efficiency is just Reach 93.4-94.5 %, and the 50th week coulombic efficiency reaches 98.8-99.6 %, charging capacity is 758.8-803.6 mAh/g
The above is only a preferred embodiment of the present invention, it is noted that those skilled in the art are come It says, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations are also answered It is considered as protection scope of the present invention.

Claims (6)

1. a kind of preparation method of lithium ion cell nano silicon monoxide composite cathode material, feature include the following steps:
(1) gaseous organic carbon source is used, by the method for chemical vapor deposition, is mixed with nano-silicon and nano oxidized sub- silicon, Then ball milling obtains nanoscale carbonization composite material
(2) composite material is poured into deionized water and is stirred evenly, obtain suspension, resulting suspension is poured into sand mill It is sanded, is then spray-dried, remove moisture removal, obtain dry mixture；
(3) under inert gas protection by mixture obtained in step (2), by staged temperature reaction, Compound Negative is obtained Pole material, is then placed in planetary ball mill and is crushed, and obtains lithium ion cell nano silicon monoxide composite cathode material.
2. a kind of preparation method according to claim 1, characterized in that the partial size of nano-silicon is 10-30nm, aoxidizes sub- silicon Partial size be 20-50nm.
3. a kind of preparation method according to claim 1, characterized in that the revolving speed of ball milling is 500 revs/min in step 1 Clock, time are for 24 hours.
4. a kind of preparation method according to claim 1, characterized in that staged temperature reaction specifically: protected in nitrogen It is first warming up to 120-150 DEG C, isothermal reaction 3h under shield, then is warming up to 1000-1200 DEG C, isothermal reaction 12-24h.
5. a kind of preparation method according to claim 4, characterized in that heating rate is 10-100 DEG C/min.
6. a kind of preparation method according to claim 1, characterized in that the revolving speed of ball mill is 300r/min in step 3.
CN201810911414.8A 2018-08-11 2018-08-11 A kind of preparation method of lithium ion cell nano silicon monoxide composite cathode material Withdrawn CN108963238A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108023072A (en) * 2017-11-29 2018-05-11 北京化工大学 A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof
CN108232151A (en) * 2017-12-29 2018-06-29 惠州亿纬锂能股份有限公司 A kind of high power capacity composite negative pole material, preparation method and include its lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108023072A (en) * 2017-11-29 2018-05-11 北京化工大学 A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof
CN108232151A (en) * 2017-12-29 2018-06-29 惠州亿纬锂能股份有限公司 A kind of high power capacity composite negative pole material, preparation method and include its lithium ion battery

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