CN102136567A - 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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- CN102136567A CN102136567A CN2011100374468A CN201110037446A CN102136567A CN 102136567 A CN102136567 A CN 102136567A CN 2011100374468 A CN2011100374468 A CN 2011100374468A CN 201110037446 A CN201110037446 A CN 201110037446A CN 102136567 A CN102136567 A CN 102136567A
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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, pyrophosphate alloy bath adding and ultrasonic dispersion; 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 lithium ion battery tin nickel carbon compound cathode materials.
Background technology
Because energy scarcity and city environmental pollution are serious day by day, seek and substitute alternative energy source oil, environment-protecting clean, solve the air pollution in city, be the social concern that presses for solution that the present 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, the electric automobile that various countries fall over each other to develop, hybrid vehicle 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 special advantages.Anode and cathode active materials and electrode fabrication are the keys of control lithium ion battery performance in the battery, have become domestic and international researcher's common recognition.
The graphite powder becomes the main body of present lithium cell cathode material so that its processing technology is simple relatively, cost is low, lithium ion storage capacity and cycle charge-discharge ability preferably.But graphite powder theoretical specific capacity is little, and the capacity attenuation rate is bigger, and high-rate charge-discharge capability is relatively poor, impels people to seek excellent more lithium ion battery negative material.From electrode fabrication, large-scale application mainly is the coating rolling process in what produce, this technology is simple, cost is low, but coating is a little less than adhesion on the collector, in the cyclic process, especially in high-power charge and discharge process, the negative material of coating comes off easily repeatedly, shorter battery life, use cost increases substantially.
Nearly one or two years, relevant for the relevant report of oxide cathode material, ashbury metal and ashbury metal-carbon compound cathode preparation and performance study, 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 easily scale, strong with the collector adhesion of electrodeposition process technology has important researching value, but present electrodeposition technology standard instability, carbon content is low in the coating, is difficult to be applied.
In sum, the main body of negative material remains the graphite powder at present, research and development have higher charge storage capacity and cycle performance, combine good tin nickel/graphite composite negative pole preparation technology and chemical property thereof with collector, are to realize the high-power important channel that discharges and recharges of lithium battery.
Summary of the invention
Technical assignment of the present invention is at above weak point, the preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials that provide a kind of and utilize prepared by electrodeposition tin nickel carbon compound cathode materials, cost is low, preparation technology is simple, chemical property is good, the life-span is long.
The technical solution adopted for the present invention to solve the technical problems is: use electrodeposition technology to prepare lithium ion battery tin nickel carbon compound cathode materials; Electrodeposition technology is:
Technology (1): graphite powder → surface chemical modification processing → adding pyrophosphate alloy electroplating bath → ultrasonic wave disperses;
Technology (2): Copper Foil collector → activation processing;
Technology (3): the Copper Foil collector that technology (2) is obtained at last is a negative electrode, is anode with the hard graphite cake, and the plating bath that obtains with technology (1) is an electrolyte, carries out the electro-deposition plated film, obtains composite deposite at last.
Described graphite powder granularity is 5～12 μ m.Adopt ball grinding method that graphite is handled, obtaining granularity is the graphite powder of 5～12 μ m.
Described graphite powder → surface chemical modification treatment process is: content of graphite is 15gL in plating bath
-1Condition under, select 1.0～1.4gL for use
-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
-1Pyrophosphate alloy electroplating bath pH is 7.5～8.5.
Described electro-deposition plated film is an anode with graphite, and the Copper Foil collector is a negative electrode, and in the plating process, current density is 1～1.4Adm
-2, 55 ℃～60 ℃ of temperature.
Described last acquisition composite deposite content is 38%～56% Sn, 27%～56% Ni, 6%～17% graphite.
Described composite deposite is under the 0.2C charge-discharge mechanism, and capacity density reaches 600mA.h.g first
-1More than, efficiency for charge-discharge is that discharge capacity remains on 250mA.h.g after 85%, two ten circulation
-1About, efficiency for charge-discharge remains on 90%.
Before the described electrodeposition technology, adopt ball grinding method that graphite is carried out preliminary treatment, obtaining granularity is the graphite powder of 5～12 μ m.Because the density of graphite is bigger than the density of electrolyte, graphite granule can sink with certain speed under action of gravity, simultaneously also can be subjected to the buoyancy that electrolyte makes progress to it, therefore the particle diameter of graphite is very big to the influence of graphite in plating bath, and the particle diameter that reduces graphite is effectively to reducing sinking speed.Graphite suspends in plating bath equably, can be the even distribution of graphite in coating and creates favorable conditions.
The graphite powder physical efficiency is evenly not wetting with plating bath to be the prerequisite that realizes alloy layer and graphite 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 effect in plating bath is the angle of wetting that reduces graphite surface, make the graphite powder positively charged, make the graphite powder easier to cathodic deposition.Content of graphite is 15gL in plating bath
-The time, the best group of composite dispersing agent becomes softex kw 1.0～1.4gL
-1, nonionic surface active agent 0.8～1.0gL such as peregal
-1, neutral electrolyte NaCl4～6gL
-1After this composite dispersing agent processing, it is stable that the emulsion that graphite powder and plating bath 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, be anode with graphite, the Copper Foil collector is a 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 a negative pole, with the lithium hexafluoro phosphate is electrolyte, form button lithium battery, test its chemical property by the battery parameter tester, under 0.2C mechanism, specific capacity reaches 600mA.h.g～more than 1 first, efficiency for charge-discharge discharge capacity after 85%, two ten circulation remains on about 250mA.h.g-1, 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, shaped (can make chip solid as requested), soluble in water, ethanol, ethylene glycol etc., cloud point is arranged, and 1% aqueous ph value is neutral.Acidproof, alkaline-resisting, the anti-hard water of energy, heat-resisting, anti-heavy metallic salt.Have good wet performance, and have emulsification preferably, dispersion, performance such as clean.
The preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials of the present invention compares with prior art, have the following advantages: the technological specification that has proposed prepared by electrodeposition lithium battery tin-nickel alloy-carbon compound cathode, forming with the ashbury metal on copper pool collector is continuous phase, with the graphite powder is the firm of disperse phase, evenly, stable composite deposite, the double dominant of performance metal and graphite powder store charge, improved the surface topography of alloy layer densification, and form metallurgical binding with collector, the acquisition adhesion is strong, chemical property is good, the long-life lithium battery negative pole is to adapt to the high-power needs that discharge and recharge of battery; Not only technology is simple, and cost is low, and is easy to accomplish scale production.
Embodiment
The preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials of the present invention uses electrodeposition technology to prepare lithium ion battery tin nickel carbon compound cathode materials; Electrodeposition technology is:
Technology (1): graphite powder → surface chemical modification processing → adding pyrophosphate alloy electroplating bath → ultrasonic wave disperses;
Technology (2): Copper Foil collector → activation processing;
Technology (3): the Copper Foil collector that technology (2) is obtained at last is a negative electrode, is anode with the hard graphite cake, and the plating bath that obtains with technology (1) is an electrolyte, carries out the electro-deposition plated film, obtains composite deposite at last.
The graphite powder granularity is 5～12 μ m.Adopt ball grinding method that graphite is handled, obtaining granularity is the graphite powder of 5～12 μ m.
The surface chemical modification treatment process is: content of graphite is 15gL in plating bath
-1Condition under, select 1.0～1.4gL for use
-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.
The 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
-1Pyrophosphate alloy electroplating bath pH is 7.5～8.5.
The electro-deposition plated film is an anode with graphite, and the Copper Foil collector is a negative electrode, and in the plating process, current density is 1～1.4Adm
-2, 55 ℃～60 ℃ of temperature.
Obtain composite deposite content at last and be 38%～56% Sn, 27%～56% Ni, 6%～17% graphite.
Composite deposite is under the 0.2C charge-discharge mechanism, and capacity density reaches 600mA.h.g first
-1More than, efficiency for charge-discharge is that discharge capacity remains on 250mA.h.g after 85%, two ten circulation
-1About, efficiency for charge-discharge remains on 90%.
Before the electrodeposition technology, to adopting ball grinding method graphite is carried out preliminary treatment, obtaining granularity is the graphite powder of 5～12 μ m.Because the density of graphite is bigger than the density of electrolyte, graphite granule can sink with certain speed under action of gravity, simultaneously also can be subjected to the buoyancy that electrolyte makes progress to it, therefore the particle diameter of graphite is very big to the influence of graphite in plating bath, and the particle diameter that reduces graphite is effectively to reducing sinking speed.Graphite suspends in plating bath equably, can be the even distribution of graphite in coating and creates favorable conditions.
The graphite powder physical efficiency is evenly not wetting with plating bath to be the prerequisite that realizes alloy layer and graphite powder codeposition, the present invention is by methods such as orthogonal tests, all kinds of dispersants have been screened, nonionic surface active agent, neutral sodium chloride such as final definite softex kw, peregal form composite dispersing agent, its main effect in plating bath is the angle of wetting that reduces graphite surface, make the graphite powder positively charged, make the graphite powder easier to cathodic deposition.Content of graphite is 15gL in plating bath
-The time, the best group of composite dispersing agent becomes softex kw 1.0～1.4gL
-1, nonionic surface active agent 0.8～1.0gL such as peregal
-1, neutral electrolyte NaCl4～6gL
-1After this composite dispersing agent processing, it is stable that the emulsion that graphite powder and plating bath 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, be anode with graphite, the Copper Foil collector is a 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 a negative pole, with the lithium hexafluoro phosphate is electrolyte, form button lithium battery, test its chemical property by the battery parameter tester, under 0.2C mechanism, specific capacity reaches 600mA.h.g～more than 1 first, efficiency for charge-discharge discharge capacity after 85%, two ten circulation remains on about 250mA.h.g～1, and efficiency for charge-discharge remains on 90%.
Except that the described technical characterictic of specification, be the known technology of those skilled in the art.
Claims (8)
1. the preparation method of a lithium ion battery tin nickel carbon compound cathode materials is characterized in that using electrodeposition technology to prepare lithium ion battery tin nickel carbon compound cathode materials; Electrodeposition technology is:
Technology (1): graphite powder → surface chemical modification processing → adding pyrophosphate alloy electroplating bath → ultrasonic wave disperses;
Technology (2): Copper Foil collector → activation processing;
Technology (3): the Copper Foil collector that technology (2) is obtained at last is a negative electrode, is anode with the hard graphite cake, and the plating bath that obtains with technology (1) is an electrolyte, carries out the electro-deposition plated film, obtains composite deposite at last.
2. the preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials according to claim 1 is characterized in that the graphite powder granularity is 5～12 μ m.
3. the preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials according to claim 2 is characterized in that adopting ball grinding method that graphite is handled, and obtaining granularity is the graphite powder of 5～12 μ m.
4. the preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials according to claim 1, it is characterized in that its described graphite powder → surface chemical modification treatment process is: content of graphite is 15gL in plating bath
-1Condition under, select 1.0～1.4gL for use
-1Softex kw, nonionic surface active agent and 4～6gL
-1Neutral electrolyte NaCl form composite dispersing agent.
5. the preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials according to claim 4 is characterized in that nonionic surface active agent adopts 0.8～1.0gL
-1Peregal.
6. the preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials according to claim 1 is characterized in that its 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
-1Pyrophosphate alloy electroplating bath pH is 7.5～8.5.
7. the preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials according to claim 1 is characterized in that its described electro-deposition plated film, is anode with graphite, and the Copper Foil collector is a negative electrode, and in the plating process, current density is 1～1.4Adm
-2, 55 ℃～60 ℃ of temperature.
8. the preparation method of a kind of lithium ion battery tin nickel carbon compound cathode materials according to claim 1 is characterized in that obtaining at last composite deposite content and is 38%～56% Sn, 27%～56% Ni, 6%～17% graphite.
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Cited By (8)
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|---|---|---|---|---|
| CN103022424A (en) * | 2012-12-21 | 2013-04-03 | 湘潭大学 | Carbon nano tube enhanced tin-nickel alloy cathode and preparation method thereof |
| CN103137956A (en) * | 2013-03-15 | 2013-06-05 | 中国计量学院 | Preparation method of nickel-tin alloy powder with porous and globular structures as lithium ion battery negative pole material |
| CN104477892A (en) * | 2014-12-12 | 2015-04-01 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of flake graphene and flake graphene device prepared by same |
| 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 |
| 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 |
| 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 |
| 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 |
| CN111366853A (en) * | 2018-12-25 | 2020-07-03 | 微宏动力***（湖州）有限公司 | Method for testing cycle performance of negative electrode material and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022424A (en) * | 2012-12-21 | 2013-04-03 | 湘潭大学 | Carbon nano tube enhanced tin-nickel alloy cathode and preparation method thereof |
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| CN103137956A (en) * | 2013-03-15 | 2013-06-05 | 中国计量学院 | Preparation method of nickel-tin alloy powder with porous and globular structures as lithium ion battery negative pole material |
| 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 |
| CN104477892A (en) * | 2014-12-12 | 2015-04-01 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of flake graphene and flake graphene device prepared by same |
| 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 |
| CN111366853A (en) * | 2018-12-25 | 2020-07-03 | 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 |
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