CN105406134B - A kind of preparation method of Si bases composite negative pole material and its lithium battery - Google Patents
A kind of preparation method of Si bases composite negative pole material and its lithium battery Download PDFInfo
- Publication number
- CN105406134B CN105406134B CN201510896670.0A CN201510896670A CN105406134B CN 105406134 B CN105406134 B CN 105406134B CN 201510896670 A CN201510896670 A CN 201510896670A CN 105406134 B CN105406134 B CN 105406134B
- Authority
- CN
- China
- Prior art keywords
- negative pole
- composite negative
- nano
- method described
- lithium battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Cu is based on the invention discloses one kindxThe Si bases composite negative pole material of O claddings and its preparation method of lithium battery, the preparation method of the lithium battery include：Step 1：The mixed hydrolysis solution of weak acid and corresponding salt of weak acid is prepared, copper source and ultrasonic dissolution is added；Step 2：Add and reacted under the nano Si particle of pretreatment, condition of water bath heating a period of time, and eccentric cleaning, it is dried to obtain Si base composite negative pole materials；Step 3：Si bases composite negative pole material and binding agent and conductive agent are uniformly mixed to get slurry according to a certain percentage；Step 4：Obtained slurry is coated on a current collector with certain thickness, certain time is dried under certain temperature, electrode slice is made, and carry out lithium battery group dress.This method preparation technology is simple, and cost is low, and the cycle performance of nano Si negative pole is significantly increased.
Description
Technical field
The present invention proposes a kind of simple CuxThe nano Si composite negative pole material of O claddings and its preparation side of lithium battery
Method, by simple hydrolysis, uniform Cu is formed in nano Si particle surfacexO clads, and by conductive with binding agent
Agent is mixed, and prepares composite cathode material for lithium ion cell.Specify CuxThe system of the nano Si composite negative pole material of O claddings
Preparation Method.
Background technology
With the fast development of information industry and new-energy automobile etc., to high-energy-density, high-specific-power, the long-life, it is low into
This demand is more and more urgent.Lithium ion battery is received much concern due to its numerous advantage as secondary energy sources field
Leading role.The development of material technology is the most important thing that performance of lithium ion battery is further lifted.Si sills are used as lithium-ion electric
Pond negative material, Li can be formed with lithium22Si5Alloy, with high power capacity (up to 4200mAhg-1) it is now commonly used
As many as ten times of graphite material.And it has relatively low removal lithium embedded current potential (about 0.1-0.3V vs Li/Li+), with electrolyte
Reactivity it is low, and cost is relatively low, the advantages of can providing very long discharge platform (Journal of Power
Sources, 163,1003,2007.).But, due in charging process Si materials can occur huge volumetric expansion (~
300%), this by cause between electrode material and electrode material and collector separation, and then electrical contact is lost, so as to cause capacity
Rapid decay, cycle performance deteriorate rapidly (Journal of The Electrochemical Society, 154, A444,
2007.).People solve the problems, such as Volume Changes of the Si materials in charge and discharge process using various methods, such as take and receive
Meter level material (Physica Status Solid-Rapid Research Letters, 4,4,2010.) is to alleviate size effect
Should, or protected with composite construction Si materials (Journal of Physical Chemol/Listry C, 111,11131,
2007 and Electrochimica Acta, 71,201,2012.) etc..Because the Si particles of nano-scale have higher table
Face activity, therefore easily reunites between particle, and is in itself to play certain mitigation for bulk effect, can not be from
Substantially solve (Chinese Science Bulletin, 57,4104,2012.).
The content of the invention
Present invention aims at provide one kind CuxThe preparation of the nano Si composite negative pole material and its lithium battery of O claddings
Method.This method preparation technology is simple, and cost is low, it is easy to accomplish, cycle performance of battery is good.
According to an aspect of the present invention, it provides a kind of based on CuxThe lithium electricity of the nano Si base composite negative pole material of O claddings
Pool preparation method, comprises the following steps：
Step 1：The mixed hydrolysis solution of weak acid and corresponding salt of weak acid is prepared, copper source and ultrasonic dissolution is added；
Step 2：Add and reacted under the nano Si particle of pretreatment, condition of water bath heating a period of time, and eccentric cleaning, do
It is dry to obtain Si base composite negative pole materials；
Step 3：Si bases composite negative pole material and binding agent and conductive agent are uniformly mixed to get slurry according to a certain percentage；
Step 4：Obtained slurry is coated on a current collector with certain thickness, certain time, system are dried under certain temperature
Into electrode slice, and carry out lithium battery group dress.
According to a further aspect of the invention, it provides a kind of CuxThe preparation side of the nano Si base composite negative pole material of O claddings
Method, the Si bases composite negative pole material is used to prepare lithium battery, and methods described includes：
Step 1：The mixed hydrolysis solution of weak acid and corresponding salt of weak acid is prepared, copper source and ultrasonic dissolution is added；
Step 2：Add and reacted under the nano Si particle of pretreatment, condition of water bath heating a period of time, and eccentric cleaning, do
It is dry to obtain Si base composite negative pole materials.
The present invention proposes to pre-process nano Si particle with HF, and reaction is hydrolyzed in acid condition, forms nanometer chi
Very little CuxThe nano Si particle of O claddings and the composite material and preparation method thereof as lithium ion battery negative material.The present invention is proposed
Above-mentioned preparation method, by simply pre-process with hydrolysis by with good electric conductivity and elasticity CuxO is uniformly wrapped
Nano Si particle surface is overlayed on, so that the volumetric expansion, raising nano Si during further alleviating material circulation are intergranular
Electric conductivity and the generation for preventing side reaction between Si particles and electrolyte.
Brief description of the drawings
In order to illustrate the particular technique content of the present invention, described in detail below in conjunction with diagram, wherein：
Fig. 1 is CuxThe nano Si composite negative pole of O claddings and its preparation method flow chart of lithium battery；
Fig. 2 is the Si and Cu of untreated Si, HF processingxThe TEM figures of the Si composites of O claddings and corresponding EDS；
Fig. 3 is CuxCharge and discharge cycles after the nano Si combination electrode and untreated Si electrode assemblings battery of O claddings are special
Property comparison diagram.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, and reference
Accompanying drawing, the present invention is described in further detail.
It is proposed by the present invention to be based on CuxThe lithium battery preparation method of the nano Si composite negative pole material of O claddings is with nano Si
Particle is original material, and by simple hydrolysis, uniform Cu is formed in nano Si particle surfacexO clads, and pass through
With binding agent, conductive agent mixing, the method for preparing composite cathode material for lithium ion cell.Preparation technology is：First by a scale
Very little nano Si particle pre-processes a period of time in certain density HF.Then CH is prepared2O2With HCOONH4Mixed solution,
Add Cu (SO4)2, ultrasonic dissolution, the nano Si particle of addition pretreatment.Under last condition of water bath heating, certain time is reacted,
Eccentric cleaning and drying.By obtained CuxThe nano Si composite negative pole of O claddings is thoroughly mixed with binding agent and conductive agent,
And be coated on copper current collector, circular electric pole piece is prepared into after drying, is compacted, and be assembled into button cell and tested.The party
Method preparation technology is simple, and cost is low, and the cycle performance of nano Si negative pole is significantly increased.
Provided in the embodiment of the present invention a kind of based on CuxIt is prepared by the lithium battery of the nano Si composite negative pole material of O claddings
Method, as shown in figure 1, comprising the following steps：
Step 1：A glass beaker is taken, a certain amount of deionized water is added, is separately added into a certain amount of weak acid and corresponding
Salt of weak acid such as CH2O2With HCOONH4Mixed solution is formed, is added homologous such as Cu (SO4)2Deng mantoquita and ultrasonic dissolution, the CH2O2
With HCOONH4Mixed solution PH between 3.7-4.5.Cu (the SO4)2Amount be 0.001mol/L-0.007mol/L；
Step 2：On the basis of step 1, the nano Si particle of pretreatment is added, when reacting one section under condition of water bath heating
Between, and with deionized water eccentric cleaning 3-5 times, and it is dried to obtain powdered composite (obtained composite negative pole material pattern
And copper content is referring to shown in 2).The bath temperature is 50 DEG C -70 DEG C, reaction time 2h-5h；The size of the nano Si particle
For 10nm-200nm.
Step 3：The composite negative pole material obtained in step 2 is uniformly mixed with binding agent and conductive agent according to a certain percentage
Uniformly obtain slurry.The ratio is 6: 3: 1-8: 1: 1；Wherein it is one in PVDF, CMC, PAA as the polymer of binding agent
Plant or several combinations；The conductive agent is one or more of in graphite, carbon black, graphene, graphite fibre, CNT
Combination.
Step 4：Obtained slurry is coated on copper current collector with certain thickness, certain time is dried under certain temperature,
Electrode slice is made, and carries out battery pack dress and test.The thickness of the film is 10 μm -500 μm, and drying temperature is 90 DEG C -120
DEG C, the time is 4h-12h.Used collector is the collector of conventional negative electrode of lithium ion battery, such as copper.
As shown in figure 3, being CuxCharge and discharge after the nano Si combination electrode and untreated Si electrode assemblings battery of O claddings
Electric cycle characteristics comparison diagram.The all reversible capacities of head of combination electrode are up to more than 3000mAh/g, and coulombic efficiency reaches 82.9%.
After 100 cycle charge-discharges, reversible capacity conservation rate is more than 62%, and reversible capacity is more than 1900mAh/g, 200 cycle charge discharges
Reversible capacity is still greater than 1500mh/g after electricity, and coulombic efficiency is up to 99.7%.The cyclicity compared with untreated nano Si electrode
It can greatly improve.
Particular embodiments described above, has been carried out further in detail to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail bright, it should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc. should be included in the protection of the present invention
Within the scope of.
Claims (11)
1. one kind is based on CuxThe lithium battery preparation method of the nano Si base composite negative pole material of O claddings, comprises the following steps：
Step 1：The mixed hydrolysis solution of weak acid and corresponding salt of weak acid is prepared, copper source and ultrasonic dissolution is added；
Step 2：Add and reacted under the nano Si particle of pretreatment, condition of water bath heating a period of time, and eccentric cleaning, dry
To Si base composite negative pole materials；
Step 3：Si bases composite negative pole material and binding agent and conductive agent are uniformly mixed to get slurry according to a certain percentage；
Step 4：Obtained slurry is coated on a current collector with certain thickness, certain time is dried under certain temperature, electricity is made
Pole piece, and carry out lithium battery group dress.
2. according to the method described in claim 1, wherein the size of the nano Si particle is 10nm-200nm.
3. according to the method described in claim 1, wherein the mixed hydrolysis solution is CH2O2And HCOONH4Mixed solution,
PH=3.7-4.5.
4. according to the method described in claim 1, wherein copper source used is Cu (SO4)2, add Cu (SO4)2Amount be
0.001mol/L-0.007mol/L。
5. according to the method described in claim 1, water bath heating temperature is 50 DEG C -70 DEG C, reaction time wherein described in step 2
For 2h-5h.
6. according to the method described in claim 1, wherein as binding agent polymer be PVDF, CMC, PAA in one kind or
Several combinations.
7. according to the method described in claim 1, wherein the conductive agent is graphite, carbon black, graphene, graphite fibre, carbon receives
One or more of combinations in mitron.
8. according to the method described in claim 1, by Si bases composite negative pole material and binding agent and conductive agent wherein in step 3
Mixed proportion is 6:3:1-8:1:1.
9. according to the method described in claim 1, the coating thickness of slurry is 10 μm -500 μm wherein described in step 4.
10. according to the method described in claim 1, drying temperature is 90 DEG C -120 DEG C wherein in step 4, the time is 4h-12h.
11. a kind of CuxThe preparation method of the nano Si base composite negative pole material of O claddings, the Si bases composite negative pole material is used to make
Standby lithium battery, methods described includes：
Step 1：The mixed hydrolysis solution of weak acid and corresponding salt of weak acid is prepared, copper source and ultrasonic dissolution is added；
Step 2：Add and reacted under the nano Si particle of pretreatment, condition of water bath heating a period of time, and eccentric cleaning, dry
To Si base composite negative pole materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510896670.0A CN105406134B (en) | 2015-12-08 | 2015-12-08 | A kind of preparation method of Si bases composite negative pole material and its lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510896670.0A CN105406134B (en) | 2015-12-08 | 2015-12-08 | A kind of preparation method of Si bases composite negative pole material and its lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105406134A CN105406134A (en) | 2016-03-16 |
| CN105406134B true CN105406134B (en) | 2017-08-25 |
Family
ID=55471487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510896670.0A Active CN105406134B (en) | 2015-12-08 | 2015-12-08 | A kind of preparation method of Si bases composite negative pole material and its lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105406134B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4848860B2 (en) * | 2006-01-13 | 2011-12-28 | ソニー株式会社 | battery |
| JP5599810B2 (en) * | 2008-11-07 | 2014-10-01 | イーグルピッチャー テクノロジーズ，エルエルシー | Non-aqueous cell is an amorphous or semi-crystalline copper-manganese oxide cathode material |
| US10366802B2 (en) * | 2009-06-05 | 2019-07-30 | University of Pittsburgh—of the Commonwealth System of Higher Education | Compositions including nano-particles and a nano-structured support matrix and methods of preparation as reversible high capacity anodes in energy storage systems |
| CN102324501B (en) * | 2011-09-09 | 2013-10-16 | 中国科学院过程工程研究所 | Silicon-based cathode composite material for lithium ion battery and preparation method thereof |
| WO2014162908A1 (en) * | 2013-03-30 | 2014-10-09 | 国立大学法人東北大学 | Negative electrode active material for lithium ion secondary batteries, method for producing same, negative electrode, and battery |
| CN103682279B (en) * | 2013-12-27 | 2016-01-27 | 浙江大学 | A kind of silica-based composite lithium ion battery cathode material and its preparation method and application |
| CN104466185A (en) * | 2014-11-12 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof |
-
2015
- 2015-12-08 CN CN201510896670.0A patent/CN105406134B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105406134A (en) | 2016-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107221716B (en) | Rechargeable aqueous zinc ion battery | |
| CN105355877B (en) | A kind of graphene metal oxide composite cathode material and preparation method thereof | |
| CN107732180B (en) | A kind of preparation method for water system sodium-ion battery anode composite material | |
| CN109921090A (en) | A kind of all solid state full battery of lithium ion and preparation method thereof | |
| CN106299275A (en) | A kind of preparation method of composite hard carbon anode material of lithium-ion battery | |
| CN106558729B (en) | A kind of lithium ion battery of graphene as anode sizing agent conductive agent | |
| CN103326007A (en) | Preparation method and application of three-dimensional graphene-based stannic oxide composite material | |
| CN107959006A (en) | A kind of lignin-base hard carbon/carbon nano tube compound material and preparation method thereof and the application in lithium ion battery negative material | |
| CN108808080B (en) | Nano composite gel electrolyte, lithium secondary battery and preparation method thereof | |
| CN104229731B (en) | Co9S8/graphene composite hydrogen storage material and preparation method thereof | |
| CN101937994A (en) | Graphene/aluminum composite cathode material of lithium ion battery and preparation method thereof | |
| CN106505200A (en) | Carbon nano tube/graphene/silicon composite lithium ion battery negative material and preparation method thereof | |
| CN106992297A (en) | A kind of preparation method and application of ternary battery composite anode material | |
| CN103236530A (en) | Silicon-carbon composite material, preparation method thereof, and lithium ion battery containing material | |
| CN106992328B (en) | The waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell | |
| CN105810947A (en) | Aluminum ion battery anode material, electrode and aluminum ion battery | |
| CN108365172A (en) | A kind of lithium an- ode material and its preparation method and application of natural polymers protection | |
| CN105870421A (en) | C-SnO2/Ti3C2 two-dimensional-nanometer negative electrode material of lithium ion battery and preparation method thereof | |
| CN108123141A (en) | A kind of three-dimensional porous foams grapheme material and its application | |
| CN107732200A (en) | A kind of method that lithium ion battery negative material is prepared using photovoltaic industry waste material | |
| Zhipeng et al. | Hierarchical porous carbon toward effective cathode in advanced zinc-cerium redox flow battery | |
| CN106025269A (en) | Method for preparing hexa-fluorine lithium ferrite and carbon nano-tube composite materials | |
| CN106159286B (en) | A kind of modified electrode and preparation method thereof applied to zinc-bromine flow battery | |
| CN105870401A (en) | Application method of graphene as conductive agent to negative electrode slurry of lithium ion battery | |
| CN104124447A (en) | Novel Co(OH)F lithium ion battery negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |