CN102136567B - Preparing method of tin-nickel-carbon composite cathode material of lithium ion battery - Google Patents
Preparing method of tin-nickel-carbon composite cathode material of lithium ion battery Download PDFInfo
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- CN102136567B CN102136567B CN201110037446.8A CN201110037446A CN102136567B CN 102136567 B CN102136567 B CN 102136567B CN 201110037446 A CN201110037446 A CN 201110037446A CN 102136567 B CN102136567 B CN 102136567B
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- graphite
- nickel
- tin
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- lithium ion
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- 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 preparing method of tin-nickel-carbon composite cathode material of a lithium ion battery, which belongs to the technical field of lithium ion batteries. The tin-nickel-carbon composite cathode material is prepared through electrodeposition process; the electrodeposition process comprises the following processes: I. conducting graphite powder, surface chemical modification treatment for the graphite powder, pyrophosphate alloy bath adding and ultrasonic dispersion for the pyrophosphate alloy bath containing the graphite powder; II. conducting copper foil current collector and activating treatment; and III. by taking the copper foil current collector obtained in the process II as a cathode, taking a hard graphite plate as a cathode and taking bath obtained in the process I as an electrolyte, performing electrodeposition film coating, to obtain a composite deposited finally. Compared with the prior art, the preparing method adopting electrodeposition to prepare the tin-nickel-carbon composite cathode material has the characteristics of low cost, simple preparing process, excellent electrochemical performance, long service life and the like.
Description
Technical field
The present invention relates to a kind of technical field of lithium ion, specifically a kind of preparation method of tin-nickel-carbon composite cathode material of lithium ion battery.
Background technology
Due to energy scarcity and city environmental pollution day by day serious, find alternative energy source petroleum replacing, environment-protecting clean, solve the air pollution in city, be the social concern in the urgent need to address that the current whole world faces, and advanced electric automobile is acknowledged as the most important mode of Future Development energy-conserving and environment-protective green traffic.Current, electric automobile, hybrid vehicle that various countries fall over each other development all need battery that power is provided, and as the supporting power supply of electric motor car, the outstanding properties of lithium ion battery has unique advantage.In battery, anode and cathode active materials and electrode fabrication are to control the key of performance of lithium ion battery, have become domestic and international researcher's common recognition.
Graphite composite powder is relatively simple with its processing technology, low, the good lithium ion storage capacity of cost and cycle charge discharge power, becomes the main body of current lithium cell cathode material.But graphite composite powder theoretical specific capacity is little, capacity attenuation rate is larger, and high-rate charge-discharge capability is poor, impels people to seek more excellent lithium ion battery negative material.From electrode fabrication, large-scale application is mainly coating rolling process in what produce, this technique is simple, cost is low, but coating is on collector a little less than adhesion, in iterative cycles process, especially, in high-power charge and discharge process, the negative material of coating easily comes off, shorter battery life, use cost increases substantially.
Nearly one or two years, relevant for the relevant report of oxide cathode material, ashbury metal and the research of ashbury metal-carbon compound cathode preparation and property, synthetic method has solid phase method, chemical reduction method, low-pressure vapor phase method, sol-gal process and electrodeposition process etc. both at home and abroad.Wherein simple, the easy scale of electrodeposition process technique, strong with collector adhesion, have important researching value, but electrodeposition technology standard is unstable at present, and in coating, carbon content is low, is difficult to be applied.
In sum, the main body of negative material remains graphite composite powder at present, research and development have higher charge storage capacity and cycle performance, are combined good tin nickel/graphite composite negative pole preparation technology and chemical property thereof with collector, are to realize the high-power important channel discharging and recharging of lithium battery.
Summary of the invention
Technical assignment of the present invention is for above weak point, and a kind of preparation method who utilizes a kind of tin-nickel-carbon composite cathode material of lithium ion battery that tin nickel carbon compound cathode materials is prepared in electro-deposition, cost is low, preparation technology is simple, chemical property is good, the life-span is long is provided.
The technical solution adopted for the present invention to solve the technical problems is: use electrodeposition technology to prepare tin-nickel-carbon composite cathode material of lithium ion battery; Electrodeposition technology is:
Technique (1): graphite composite powder → graphite composite powder is carried out to surface chemical modification processing → be added to pyrophosphate alloy electroplating bath → to adding the pyrophosphate alloy electroplating bath of graphite composite powder to carry out ultrasonic wave dispersion;
Technique (2): Copper Foil collector → activation processing;
Technique (3): the Copper Foil collector that technique (2) is finally obtained is negative electrode, take hard graphite cake as anode, and the plating solution that the technique (1) of take obtains is electrolyte, carries out electro-deposition plated film, finally obtains composite deposite.
Described graphite composite powder granularity is 5～12 μ m.Adopt ball grinding method to process graphite, obtain the graphite composite powder that granularity is 5～12 μ m.
Described graphite composite powder → graphite composite powder is carried out to surface chemical modification treatment process is: in plating solution, graphite composite powder content is 15gL
-1condition under, select 1.0～1.4gL
-1softex kw, nonionic surface active agent and 4～6gL
-1neutral electrolyte NaCl form composite dispersing agent.
Described nonionic surface active agent adopts 0.8～1.0gL
-1peregal.
Described pyrophosphate alloy electroplating bath adopts environment-friendly type pyrophosphate system, comprises NiCl
250～70gL
-1, SnCl
210～18gL
-1, K
4p
2o
7180～210gL
-1, glycine 20gL
-1; Pyrophosphate alloy electroplating bath pH is 7.5～8.5.
Described electro-deposition plated film, take hard graphite cake as anode, and Copper Foil collector is negative electrode, and in plating process, current density is 1～1.4Adm
-2, 55 ℃～60 ℃ of temperature.
The Sn that described last acquisition composite deposite quality percentage composition is 38%～56%, 27%～56% Ni, 6%～17% graphite.
Described composite deposite is under 0.2C charge-discharge mechanism, and capacity density reaches 600mA.h.g first
-1above, efficiency for charge-discharge is that after 85%, two ten circulation, discharge capacity remains on 250mA.h.g
-1left and right, efficiency for charge-discharge remains on 90%.
Before described electrodeposition technology, adopt ball grinding method to carry out preliminary treatment to graphite, obtain the graphite composite powder that granularity is 5～12 μ m.Because the density of the density ratio electrolyte of graphite is large, graphite granule can sink with certain speed under Action of Gravity Field, also can be subject to the buoyancy that electrolyte makes progress to it simultaneously, therefore the impact in plating solution is very large on graphite for the particle diameter of graphite, and the particle diameter that reduces graphite is effectively to reducing sinking speed.Graphite suspends equably in plating solution, can be graphite being uniformly distributed in coating and creates favorable conditions.
Can graphite composite powder evenly soak with plating solution is the prerequisite that realizes alloy layer and graphite composite powder codeposition, the present invention is by methods such as orthogonal tests, all kinds of dispersants have been screened, final definite softex kw, peregal, neutral sodium chloride form composite dispersing agent, its Main Function in plating solution is the angle of wetting that reduces graphite surface, make graphite composite powder positively charged, make graphite composite powder more easily to cathodic deposition.In plating solution, content of graphite is 15gL
-time, the best group of composite dispersing agent becomes softex kw 1.0～1.4gL
-1, the nonionic surface active agent 0.8～1.0gL such as peregal
-1, neutral electrolyte NaCl4～6gL
-1.After processing by this composite dispersing agent, it is stable that the emulsion that graphite composite powder and plating solution form can keep in 24 hours, and powder surface is positively charged, has effectively realized the codeposition of powder and coating.As current density 1.0～1.4Adm
-2, during 55～60 ℃ of temperature, take graphite as anode, Copper Foil collector is negative electrode, can obtain content and be respectively 38%～56% Sn, 27%～56% Ni, and the composite deposite of 6%～17%C.
Composite deposite is anodal, lithium metal is negative pole, take lithium hexafluoro phosphate as electrolyte, form button lithium battery, by battery parameter tester, test its chemical property, under 0.2C mechanism, more than specific capacity reaches 600mA.h.g～1 first, efficiency for charge-discharge discharge capacity after 85%, two ten circulation remains on 250mA.h.g-1 left and right, and efficiency for charge-discharge remains on 90%.
Peregal: AEO, levelling agent has another name called peregal, belong to nonionic surface active agent, outward appearance is milky or ecru ointment shape, when molecular weight is higher, be solid shape (can make as requested chip solid), soluble in water, ethanol, ethylene glycol etc., have cloud point, 1% aqueous ph value is neutral.Acidproof, alkaline-resisting, the resistance to hard water of energy, heat-resisting, resistance to heavy metallic salt.There is good wet performance, and there is good emulsification, dispersion, the performance such as clean.
The preparation method of a kind of tin-nickel-carbon composite cathode material of lithium ion battery of the present invention compared to the prior art, have the following advantages: proposed the technological specification that lithium battery tin-nickel alloy-carbon compound cathode is prepared in electro-deposition, on copper pool collector, form and take ashbury metal as continuous phase, what the graphite composite powder of take was disperse phase is firm, evenly, stable composite deposite, performance metal and graphite composite powder store the double dominant of electric charge, improved the surface topography of alloy layer densification, and form metallurgical binding with collector, acquisition adhesion is strong, chemical property is good, long-life lithium battery negative pole, to adapt to the high-power needs that discharge and recharge of battery, not only technique is simple, and cost is low, and is easy to accomplish scale production.
Embodiment
The preparation method of a kind of tin-nickel-carbon composite cathode material of lithium ion battery of the present invention, uses electrodeposition technology to prepare tin-nickel-carbon composite cathode material of lithium ion battery; Electrodeposition technology is:
Technique (1): graphite composite powder → graphite composite powder is carried out to surface chemical modification processing → be added to pyrophosphate alloy electroplating bath → to adding the pyrophosphate alloy electroplating bath of graphite composite powder to carry out ultrasonic wave dispersion;
Technique (2): Copper Foil collector → activation processing;
Technique (3): the Copper Foil collector that technique (2) is finally obtained is negative electrode, take hard graphite cake as anode, and the plating solution that the technique (1) of take obtains is electrolyte, carries out electro-deposition plated film, finally obtains composite deposite.
Graphite composite powder granularity is 5～12 μ m.Adopt ball grinding method to process graphite, obtain the graphite composite powder that granularity is 5～12 μ m.
Graphite composite powder is carried out to surface chemical modification treatment process is: in plating solution, graphite composite powder content is 15gL
-1condition under, select 1.0～1.4gL
-1softex kw, nonionic surface active agent and 4～6gL
-1neutral electrolyte NaCl form composite dispersing agent.
Nonionic surface active agent adopts 0.8～1.0gL
-1peregal.
Pyrophosphate alloy electroplating bath adopts environment-friendly type pyrophosphate system, comprises NiCl
250～70gL
-1, SnCl
210～18gL
-1, K
4p
2o
7180～210gL
-1, glycine 20gL
-1; Pyrophosphate alloy electroplating bath pH is 7.5～8.5.
Electro-deposition plated film, take hard graphite cake as anode, and Copper Foil collector is negative electrode, and in plating process, current density is 1～1.4Adm
-2, 55 ℃～60 ℃ of temperature.
Finally obtain the Sn that composite deposite quality percentage composition is 38%～56%, 27%～56% Ni, 6%～17% graphite.
Composite deposite is under 0.2C charge-discharge mechanism, and capacity density reaches 600mA.h.g first
-1above, efficiency for charge-discharge is that after 85%, two ten circulation, discharge capacity remains on 250mA.h.g
-1left and right, efficiency for charge-discharge remains on 90%.
Before electrodeposition technology, to adopting ball grinding method to carry out preliminary treatment to graphite, obtain the graphite composite powder that granularity is 5～12 μ m.Because the density of the density ratio electrolyte of graphite is large, graphite granule can sink with certain speed under Action of Gravity Field, also can be subject to the buoyancy that electrolyte makes progress to it simultaneously, therefore the impact in plating solution is very large on graphite for the particle diameter of graphite, and the particle diameter that reduces graphite is effectively to reducing sinking speed.Graphite suspends equably in plating solution, can be graphite being uniformly distributed in coating and creates favorable conditions.
Can graphite composite powder evenly soak with plating solution is the prerequisite that realizes alloy layer and graphite composite powder codeposition, the present invention is by methods such as orthogonal tests, all kinds of dispersants have been screened, nonionic surface active agent, the neutral sodium chloride such as final definite softex kw, peregal form composite dispersing agent, its Main Function in plating solution is the angle of wetting that reduces graphite surface, make graphite composite powder positively charged, make graphite composite powder more easily to cathodic deposition.In plating solution, content of graphite is 15gL
-time, the best group of composite dispersing agent becomes softex kw 1.0～1.4gL
-1, the nonionic surface active agent 0.8～1.0gL such as peregal
-1, neutral electrolyte NaCl4～6gL
-1.After processing by this composite dispersing agent, it is stable that the emulsion that graphite composite powder and plating solution form can keep in 24 hours, and powder surface is positively charged, has effectively realized the codeposition of powder and coating.As current density 1.0～1.4Adm
-2, during 55～60 ℃ of temperature, take graphite as anode, Copper Foil collector is negative electrode, can obtain content and be respectively 38%～56% Sn, 27%～56% Ni, and the composite deposite of 6%～17%C.
Composite deposite is anodal, lithium metal is negative pole, take lithium hexafluoro phosphate as electrolyte, form button lithium battery, by battery parameter tester, test its chemical property, under 0.2C mechanism, more than specific capacity reaches 600mA.h.g～1 first, efficiency for charge-discharge discharge capacity after 85%, two ten circulation remains on left and right, 250mA.h.g～1, and efficiency for charge-discharge remains on 90%.
Except the technical characterictic described in specification, be the known technology of those skilled in the art.
Claims (7)
1. a preparation method for tin-nickel-carbon composite cathode material of lithium ion battery, is characterized in that using electrodeposition technology to prepare tin-nickel-carbon composite cathode material of lithium ion battery; Electrodeposition technology is:
Technique (1): graphite composite powder → graphite composite powder is carried out to surface chemical modification processing → be added to pyrophosphate alloy electroplating bath → to adding the pyrophosphate alloy electroplating bath of graphite composite powder to carry out ultrasonic wave dispersion;
Technique (2): Copper Foil collector → activation processing;
Technique (3): the Copper Foil collector that technique (2) is finally obtained is negative electrode, take hard graphite cake as anode, and the plating solution that the technique (1) of take obtains is electrolyte, carries out electro-deposition plated film, finally obtains composite deposite;
Described graphite composite powder → graphite composite powder is carried out to surface chemical modification treatment process is: in plating solution, graphite composite powder content is 15gL
-1condition under, select 1.0～1.4gL
-1softex kw, nonionic surface active agent and 4～6gL
-1neutral electrolyte NaCl form composite dispersing agent.
2. the preparation method of a kind of tin-nickel-carbon composite cathode material of lithium ion battery according to claim 1, is characterized in that graphite composite powder granularity is 5～12 μ m.
3. the preparation method of a kind of tin-nickel-carbon composite cathode material of lithium ion battery according to claim 2, is characterized in that adopting ball grinding method to process graphite, obtains the graphite composite powder that granularity is 5～12 μ m.
4. the preparation method of a kind of tin-nickel-carbon composite cathode material of lithium ion battery according to claim 1, is characterized in that nonionic surface active agent adopts 0.8～1.0gL
-1peregal.
5. the preparation method of a kind of tin-nickel-carbon composite cathode material of lithium ion battery according to claim 1, is characterized in that the pyrophosphate alloy electroplating bath described in it adopts environment-friendly type pyrophosphate system, comprises NiCl
250～70gL
-1, SnCl
210～18gL
-1, L
4p
2o
7180～210gL
-1, glycine 20gL
-1; Pyrophosphate alloy electroplating bath pH is 7.5～8.5.
6. the preparation method of a kind of tin-nickel-carbon composite cathode material of lithium ion battery according to claim 1, it is characterized in that the electro-deposition plated film described in it, take hard graphite cake as anode, Copper Foil collector is negative electrode, in plating process, current density is 1～1.4Adm
-2, 55 ℃～60 ℃ of temperature.
7. the preparation method of a kind of tin-nickel-carbon composite cathode material of lithium ion battery according to claim 1, is characterized in that finally obtaining the Sn that composite deposite quality percentage composition is 38%～56%, 27%～56% Ni, 6%～17% graphite.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103022424B (en) * | 2012-12-21 | 2014-10-29 | 湘潭大学 | Carbon nano tube enhanced tin-nickel alloy cathode and preparation method thereof |
| CN103137956B (en) * | 2013-03-15 | 2015-08-12 | 中国计量学院 | The lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic |
| CN104477892B (en) * | 2014-12-12 | 2016-08-24 | 盐城市新能源化学储能与动力电源研究中心 | Flaky graphite alkene device prepared by the preparation method of a kind of flaky graphite alkene and use the method |
| CN104835946A (en) * | 2015-05-30 | 2015-08-12 | 田东 | Tin and carbon composite cathode material of lithium ion battery and preparation method of tin and carbon composite cathode material |
| CN106654171A (en) * | 2015-10-29 | 2017-05-10 | 深圳市比克动力电池有限公司 | A composite dispersant, lithium ion battery anode slurry, an anode and a lithium ion battery |
| CN106601993A (en) * | 2016-12-29 | 2017-04-26 | 深圳市沃特玛电池有限公司 | Lithium ion battery negative electrode plate and preparation method therefor |
| CN111366853B (en) * | 2018-12-25 | 2023-02-10 | 微宏动力***（湖州）有限公司 | Method for testing cycle performance of negative electrode material and application thereof |
| CN110364736A (en) * | 2019-07-12 | 2019-10-22 | 大连恒超锂业科技有限公司 | A kind of cathode of lithium battery slurry and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529368A (en) * | 2003-10-17 | 2004-09-15 | 清华大学 | Method for synthesizing lithiumion cell negative electrode material |
| JP2005108440A (en) * | 2003-03-24 | 2005-04-21 | Samsung Sdi Co Ltd | Electrolyte for lithium secondary battery, and lithium secondary battery including it |
| CN1738077A (en) * | 2005-09-06 | 2006-02-22 | 天津力神电池股份有限公司 | Method for preparing negative pole material of lithium ion cell high-capacity tin composite |
| TW200713671A (en) * | 2005-09-28 | 2007-04-01 | Univ Nat Tsing Hua | Modification and preparation method of negative electrode material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8367251B2 (en) * | 2007-08-30 | 2013-02-05 | Sony Corporation | Anode with lithium containing ionic polymer coat, method of manufacturing same, secondary battery, and method of manufacturing same |
-
2011
- 2011-02-14 CN CN201110037446.8A patent/CN102136567B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005108440A (en) * | 2003-03-24 | 2005-04-21 | Samsung Sdi Co Ltd | Electrolyte for lithium secondary battery, and lithium secondary battery including it |
| CN1529368A (en) * | 2003-10-17 | 2004-09-15 | 清华大学 | Method for synthesizing lithiumion cell negative electrode material |
| CN1738077A (en) * | 2005-09-06 | 2006-02-22 | 天津力神电池股份有限公司 | Method for preparing negative pole material of lithium ion cell high-capacity tin composite |
| TW200713671A (en) * | 2005-09-28 | 2007-04-01 | Univ Nat Tsing Hua | Modification and preparation method of negative electrode material |
Non-Patent Citations (2)
| Title |
|---|
| "锂离子电池负极碳复合材料的制备与性能研究";孙杨正;《上海交通大学硕士学位论文》;20031231(第2003年期);正文第17页第1段到第28段第1段 * |
| 孙杨正."锂离子电池负极碳复合材料的制备与性能研究".《上海交通大学硕士学位论文》.2003,(第2003年期), |
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