CN106058152A - Cu-doped SnOx negative electrode and preparation method thereof - Google Patents

Cu-doped SnOx negative electrode and preparation method thereof Download PDF

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Publication number
CN106058152A
CN106058152A CN201610056054.9A CN201610056054A CN106058152A CN 106058152 A CN106058152 A CN 106058152A CN 201610056054 A CN201610056054 A CN 201610056054A CN 106058152 A CN106058152 A CN 106058152A
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Prior art keywords
snox
negative pole
preparation
target
layer
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CN201610056054.9A
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Inventor
石先兴
王慧敏
严红
吕豪杰
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Universal A 1 System Co Ltd
Wanxiang Group Corp
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Universal A 1 System Co Ltd
Wanxiang Group Corp
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a Cu-doped SnOx negative electrode. The negative electrode uses porous foamed nickel as a substrate material; a Cu-doped Sn film is plated on the surface of the porous foamed nickel, the mass of Cu is 2 to 5% of Sn, a layer of aluminum is sputtered on the porous foamed nickel by using a magnetron sputtering method at first, and then a layer of niobium is sputtered; and then a Cu sheet is placed on a sputtering area, and a target material is a circular metal Sn target. According to the invention, doping of Cu inhibits growth of SnOx film clusters, so a surface crystal grain size becomes smaller, and the contact area of the negative electrode and an electrolyte increases, which facilitates rapid embedding of lithium ions; moreover, the surface crystal grain size becomes smaller and changes of the absolute volume of each particle in charging and discharging are small, so volume expansion during embedding of lithium ions into SnOx is alleviated, and cycle stability of the SnOx negative electrode can be substantially improved.

Description

The SnOx negative pole of a kind of Cu that adulterates and preparation method
Technical field
The present invention relates to the preparation field of energy and material, relate to a kind of simple effectively, slow down volumetric expansion when SnOx embeds lithium ion, significantly improve SnOx negative pole and the preparation method of the doping Cu of SnOx negative pole cyclical stability.
Background technology
Tin base cathode material includes metal Sn, oxide S nOx(tin-based oxide SnO2 and SnO can reversibly store up lithium, both tin-oxides are referred to as SnOx), pink salt SnSO4 etc., tin-based material has obvious advantage as lithium ion battery negative material: 1. specific capacity is high, and theoretical lithium storage content reaches 994mAh/g；2. storage lithium current potential is higher than the deposition potential of lithium metal, and during high current charge-discharge, the deposition of lithium metal is inhibited；3. charge and discharge process does not exist solvent imbedding problem altogether, so solvent type selecting limit is less；4. Sn sill density is big, and therefore its volume and capacity ratio has more advantage compared with other existing negative materials；5. low price.
The method preparing tin oxide film at present is a lot, mainly has sol-gel process, thermal evaporation, magnetron sputtering method, chemical vapour deposition technique etc..Sn-polymetallic orefield prepared by distinct methods has different granular sizes and surface topography, and in charge and discharge process, the change in volume difference of tin-oxide is relatively big, and reversible capacity and cyclical stability are had large effect.Belliard et al. proposition SnOx negative pole of ball-milling method manufacture doping Zn, but cyclical stability is poor.
During the subject matter of tin-oxide negative material is material removal lithium embedded, material itself can occur change in volume to cause electrode efflorescence, lithium storage content loop attenuation.And metallic tin is the most soft, being easily gathered into cluster, cluster will cause occurring in material two-phase section, produce volume in cyclic process and not mate, and these can cause the decay of material reversible specific capacity, and cyclical stability is deteriorated.
Summary of the invention
It is an object of the invention to easily be gathered into cluster during solving existing tin-oxide negative material removal lithium embedded, cause the decay of material reversible specific capacity, defect that cyclical stability is deteriorated and provide a kind of simple effectively, slow down volumetric expansion when SnOx embeds lithium ion, significantly improve SnOx negative pole and the preparation method of the doping Cu of SnOx negative pole cyclical stability.
To achieve these goals, the present invention is by the following technical solutions:
The SnOx negative pole of a kind of Cu that adulterates, described negative pole is with porous foam nickel as backing material, and at the Sn thin film of porous foam nickel surface plating doping Cu, the quality of Cu is the 2-5% of the quality of Sn.In the technical program, by magnetically controlled sputter method preparation doping Cu tin-based oxide thin film material, the growth of SnOx crystal grain is inhibited by doping Cu, amorphous Sn Ox thin-film material has more preferable cycle performance, because amorphous structure can preferably discharge reacts produced internal stress with Li.Additionally, the crack that film surface compared to the Cu that do not adulterates is slight, crystalline particle is relatively big, and agglomeration is the most obvious.After doping Cu, SnOx granule is less, arranges more uniform.Between granule, contact is good, and this structure has more preferable electron conduction.
As preferably, the thickness of Sn thin film is 400-600nm.
As preferably, before porous foam nickel surface plating Sn layer, first plating thickness is the aluminum of 100-200nm, then plates the niobium that a layer thickness is 200-400nm.
The preparation method of the SnOx negative pole of a kind of Cu that adulterates, described preparation method comprises the following steps: first sputters one layer of aluminum on porous foam nickel with magnetron sputtering method, then sputters one layer of niobium；Then placing Cu sheet in sputter area, target is circular metal Sn target.In the technical program, Sn base complex is made up of active center Sn-O bonding random network around, and random grid is made up of the Cu adulterated, and Cu makes that Sn-O center is mutually isolated comes, effectively suppress growing up and interparticle reunion of SnO2 granule, electrode efflorescence therefore can be suppressed to lose efficacy.
As preferably, magnetron sputtering power is 200-500W, and atmosphere is the gaseous mixture of oxygen and argon, and oxygen and argon flow amount are than for 2:1, operating pressure 0.65-0.7Pa, and temperature is 28-32 DEG C, and sputtering time is 80-100min.
As preferably, a diameter of 110mm of circular metal Sn target, the area of circular metal Sn target and the area ratio of Cu sheet are 8-12:1.
As preferably, the thickness of aluminium lamination is 100-200nm, and the thickness of niobium layer is 200-400nm.
The invention has the beneficial effects as follows:
1) doping Cu inhibits the growth of SnOx thin film cluster so that surface grain size diminishes, and material increases with electrolyte contacts area, and beneficially lithium ion quickly embeds；Additionally, surface particles size diminishes, the absolute volume change in charge and discharge process of each granule is less, slow down volumetric expansion when SnOx embeds lithium ion, can significantly improve SnOx negative pole cyclical stability；
2) Sn base complex is made up of active center Sn-O bonding random network around, random grid is made up of the Cu adulterated, Cu makes that Sn-O center is mutually isolated comes, effectively the growing up and interparticle reunion of suppression SnO2 granule, and electrode efflorescence therefore can be suppressed to lose efficacy；
3) magnetically controlled sputter method prepares SnOx thin film, it is achieved the doping ratio controllable adjustment of Cu, the method is the most effective.
Accompanying drawing explanation
Fig. 1 is the cycle performance of battery comparison diagram that the battery that embodiment 1-2 is made is made with comparative example 1.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described in detail, but this explanation is not intended that the improper restriction to technical solution of the present invention.
Magnetron sputtering of the present invention uses the JGP560C15 type magnetron sputtering coating system of Shenyang Teng Ao vacuum technique company limited.
Embodiment 1
A kind of preparation method of the SnOx negative pole of the Cu that adulterates, described preparation method comprises the following steps: first sputters, with magnetron sputtering method, the aluminum that a layer thickness is 100nm on porous foam nickel, then sputters the niobium that a layer thickness is 200nm；Then placing Cu sheet in sputter area, target is circular metal Sn target；The thickness of Sn thin film is 400nm；Magnetron sputtering power is 200W, and atmosphere is the gaseous mixture of oxygen and argon, and oxygen and argon flow amount are than for 2:1, operating pressure 0.65Pa, and temperature is 28 DEG C, and sputtering time is 80min；A diameter of 110mm of circular metal Sn target, the area of circular metal Sn target and the area ratio of Cu sheet are 8:1；The quality of Cu is the 2% of the quality of Sn.
The film sample sputtered in porous foam nickel substrate being put into glove box, does electrode and reference electrode with metal lithium sheet, thickness is 25 microns of PE barrier films, electrolyte 1.15M LiPF6/EC+DMC(1:1), additive is the FEC of 2%.Simulated battery is assembled in argon gas atmosphere.
Embodiment 2
A kind of preparation method of the SnOx negative pole of the Cu that adulterates, described preparation method comprises the following steps: first sputters, with magnetron sputtering method, the aluminum that a layer thickness is 150nm on porous foam nickel, then sputters the niobium that a layer thickness is 300nm；Then placing Cu sheet in sputter area, target is circular metal Sn target；The thickness of Sn thin film is 500nm；Magnetron sputtering power is 300W, and atmosphere is the gaseous mixture of oxygen and argon, and oxygen and argon flow amount are than for 2:1, operating pressure 0.68Pa, and temperature is 30 DEG C, and sputtering time is 100min；A diameter of 110mm of circular metal Sn target, the area of circular metal Sn target and the area ratio of Cu sheet are 10:1；The quality of Cu is the 5% of the quality of Sn.
The film sample sputtered in porous foam nickel substrate being put into glove box, does electrode and reference electrode with metal lithium sheet, thickness is 25 microns of PE barrier films, electrolyte 1.15M LiPF6/EC+DMC(1:1), additive is the FEC of 2%.Simulated battery is assembled in argon gas atmosphere.
Embodiment 3
A kind of preparation method of the SnOx negative pole of the Cu that adulterates, described preparation method comprises the following steps: first sputters, with magnetron sputtering method, the aluminum that a layer thickness is 200nm on porous foam nickel, then sputters the niobium that a layer thickness is 400nm；Then placing Cu sheet in sputter area, target is circular metal Sn target；The thickness of Sn thin film is 600nm；Magnetron sputtering power is 500W, and atmosphere is the gaseous mixture of oxygen and argon, and oxygen and argon flow amount are than for 2:1, operating pressure 0.7Pa, and temperature is 32 DEG C, and sputtering time is 100min；A diameter of 110mm of circular metal Sn target, the area of circular metal Sn target and the area ratio of Cu sheet are 12:1；The quality of Cu is the 3.5% of the quality of Sn.
The film sample sputtered in porous foam nickel substrate being put into glove box, does electrode and reference electrode with metal lithium sheet, thickness is 25 microns of PE barrier films, electrolyte 1.15M LiPF6/EC+DMC(1:1), additive is the FEC of 2%.Simulated battery is assembled in argon gas atmosphere.
Comparative example 1, undoped p copper, aluminum, niobium, directly tin plating in substrate, step is same as in Example 1.
Embodiment 1-2 and comparative example 1 being obtained simulated battery and carries out test, test voltage scope: 0.005V-1.0V at the BTS2000 type discharge and recharge instrument of Neware, result is shown in Fig. 1.
It can be seen from figure 1 that undoped p sample initial discharge capacity 604mAh/g, residual capacity conservation rate 78% after 30 circulations；Doping Cu is 2% sample initial discharge capacity 598mAh/g, residual capacity conservation rate 84.2% after 30 circulations；Doping Cu is 5% sample initial discharge capacity 584mAh/g, residual capacity conservation rate 92.8% after 30 circulations.
It should be noted that the listed above specific embodiment being only the present invention, it is clear that the invention is not restricted to above example, have the similar change of many therewith.If all deformation that those skilled in the art directly derives from present disclosure or associates, protection scope of the present invention all should be belonged to.

Claims (7)

1. the SnOx negative pole of the Cu that adulterates, it is characterised in that described negative pole is with porous foam nickel as backing material, and at the Sn thin film of porous foam nickel surface plating doping Cu, the quality of Cu is the 2-5% of the quality of Sn.
The SnOx negative pole of a kind of Cu that adulterates the most according to claim 1, it is characterised in that the thickness of Sn thin film is 400-600nm.
The SnOx negative pole of a kind of Cu that adulterates the most according to claim 1, it is characterised in that before porous foam nickel surface plating Sn layer, first plating thickness is the aluminum of 100-200nm, then plates the niobium that a layer thickness is 200-400nm.
4. the preparation method of the SnOx negative pole of a doping Cu as claimed in claim 1, it is characterised in that described preparation method comprises the following steps: first sputters one layer of aluminum on porous foam nickel with magnetron sputtering method, then sputters one layer of niobium；Then placing Cu sheet in sputter area, target is circular metal Sn target.
The preparation method of the SnOx negative pole of a kind of Cu that adulterates the most according to claim 4, it is characterized in that, magnetron sputtering power is 200-500W, atmosphere is the gaseous mixture of oxygen and argon, oxygen and argon flow amount are than for 2:1, operating pressure 0.65-0.7Pa, temperature is 28-32 DEG C, and sputtering time is 80-100min.
The preparation method of the SnOx negative pole of a kind of Cu that adulterates the most according to claim 4, it is characterised in that a diameter of 110mm of circular metal Sn target, the area of circular metal Sn target and the area ratio of Cu sheet are 8-12:1.
The preparation method of the SnOx negative pole of a kind of Cu that adulterates the most according to claim 4, it is characterised in that the thickness of aluminium lamination is 100-200nm, the thickness of niobium layer is 200-400nm.
CN201610056054.9A 2016-01-27 2016-01-27 Cu-doped SnOx negative electrode and preparation method thereof Pending CN106058152A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101339989A (en) * 2008-06-10 2009-01-07 华南师范大学 Aluminum-tin alloy film for lithium ionic cell negative electrode and method for preparing the same
CN102110807A (en) * 2011-01-27 2011-06-29 东莞市迈科科技有限公司 Preparation method of tin oxide/carbon nano tube composite negative electrode material and application of material
CN103904300A (en) * 2014-03-14 2014-07-02 南开大学 Tin-based composite thin film material for lithium ion battery as well as preparation method and application of thin film material
CN104576087A (en) * 2015-02-03 2015-04-29 哈尔滨工业大学 Production method of electrode of supercapacitor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101339989A (en) * 2008-06-10 2009-01-07 华南师范大学 Aluminum-tin alloy film for lithium ionic cell negative electrode and method for preparing the same
CN102110807A (en) * 2011-01-27 2011-06-29 东莞市迈科科技有限公司 Preparation method of tin oxide/carbon nano tube composite negative electrode material and application of material
CN103904300A (en) * 2014-03-14 2014-07-02 南开大学 Tin-based composite thin film material for lithium ion battery as well as preparation method and application of thin film material
CN104576087A (en) * 2015-02-03 2015-04-29 哈尔滨工业大学 Production method of electrode of supercapacitor

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
K.-F. CHIU 等: "Structural Evolution and Electrochemical Performance of Sputter-Deposited Cu6Sn5 Thin-Film Anodes", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 *
PAN OUYANGA等: "Electrochemical & microstructural investigations of magnetronsputtered nanostructured ATO thin films for application in Li-ion battery", 《ELECTROCHIMICA ACTA》 *
刘畅 等: "微型薄膜锂离子电池负极材料SnOx掺杂Cu研究", 《传感器与微系统(TRANSDUCER AND MICROSYSTEM TECHNOLOGIES)》 *

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Application publication date: 20161026