CN104393237B - Stannum-base alloy negative plate for lithium ion battery and preparation method thereof - Google Patents

Stannum-base alloy negative plate for lithium ion battery and preparation method thereof Download PDF

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CN104393237B
CN104393237B CN201410519378.2A CN201410519378A CN104393237B CN 104393237 B CN104393237 B CN 104393237B CN 201410519378 A CN201410519378 A CN 201410519378A CN 104393237 B CN104393237 B CN 104393237B
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electroplate liquid
base alloy
plate
plating
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CN104393237A (en
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杨书廷
刘玉霞
张会双
乔芸
董红玉
王秋娴
尹艳红
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Henan Normal University
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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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • 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
    • 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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  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Electroplating Methods And Accessories (AREA)
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Abstract

The invention discloses a stannum-base alloy negative plate for a lithium ion battery and a preparation method thereof. The stannum-base alloy negative plate is prepared according to the following method: 1) getting an electroplating solution main salt and preparing an electroplating solution A containing stannum ion and copper ion; 2) adding an additive into the electroplating solution A to obtain an electroplating solution B; 3) performing combination-surface isolation-layer processing on a cathode employed by electroplating; 4) putting the electroplating solution B into an electroplating tank for electroplating, so as to form an alloy crude plate on the cathode surface; and 5) stripping the alloy crude plate from the cathode surface and performing post-processing, so as to obtain the stannum-base alloy negative plate. The stannum-base alloy negative plate for the lithium ion battery gives consideration to both an active substances and a current collector, saves a conventional current collector, has high energy density and high volume density, and solves the problem that the active substance fall off from the current collector in a charge/discharge cycling process. The preparation method is simple in preparation process and convenient to operate, saves cost, and is time-saving, labor-saving, relatively strong in operability and suitable for large-scale industrial production.

Description

A kind of lithium ion battery tin base alloy anode plate and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery tin base alloy anode plate, Also relate to a kind of preparation method of lithium ion battery tin base alloy anode plate.
Background technology
As social development in science and technology, particularly lithium ion battery are in the wide of the aspect such as portable electric appts and electric automobile General application, exploitation high power capacity, long-life battery are extremely urgent.At present business-like lithium ion battery negative mainly adopts carbon materials Material, its theoretical specific capacity is 372mAh/g, and it is limited that the material with carbon element specific capacity of commercial Application is improved, meanwhile, in application process In, graphitized carbon material protective layer can decompose when temperature is higher, cause battery failure or cause safety problem.Present business The lithium ion electronics negative pole of product cannot meet the needs of contemporary electronic industry development, thus select a kind of high-energy-density and The negative material of safety is the target of electrochemical operation.
Tin-based material is used as ion cathode material lithium, the energy density of Yin Qigao, low discharge platform and preferable conduction Property and widely paid close attention to.Due to stannum, change in volume is larger during battery cycle charge-discharge, causes it easily from afflux Come off on body and efflorescence, so as to cause cycle performance of battery decline and stability test it is poor the problems such as.It is above-mentioned in order to solve Problem, prior art is typically solved by three kinds of modes：(1) will be combined with other materials after stannum nanorize；(2) build nucleocapsid or The tin composite material of person's hollow-core construction；(3) kamash alloy is prepared.By it is substantial amounts of research and it was verified that the third method most For convenience of feasible.In recent years, there is substantial amounts of report with regard to the negative pole preparation method of kamash alloy, is mainly concerned with electronation Method, sputtering method, means of electron beam deposition, fusion method, electrodeposition process etc., above method either prepares nanometer tin composite material still Tin Composite Material is deposited on a current collector, there is active substance stannum during charge and discharge cycles, take off easily from collector The problem for falling.
The content of the invention
It is an object of the invention to provide a kind of lithium ion battery tin base alloy anode plate, solves stannum in existing stannum negative pole and holds The problem for easily coming off from collector.
Second object of the present invention is to provide a kind of preparation method of lithium ion battery tin base alloy anode plate
In order to realize object above, the technical solution adopted in the present invention is：A kind of lithium ion battery is negative with kamash alloy Pole plate, the tin base alloy anode plate is prepared by following methods：
1) the main salt of power taking plating solution, prepare containing tin ion concentration be 0.05～0.5mol/L, copper ion concentration be 0.06～ The electroplate liquid A of 0.6mol/L；
2) additive is added in electroplate liquid A, obtains electroplate liquid B；
3) negative electrode used to plating is combined face isolated chromatography layer and processes, and makes cathode surface form combination interface isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, in cathode surface the thick plate of alloy is formed；
5) the thick plate of alloy is carried out into post processing from after cathode surface stripping, is obtained final product.
The main salt of the electroplate liquid is pink salt and mantoquita.As the preferred ditin diphosphate of pink salt or SnSO of the main salt of electroplate liquid4。 As the preferred Copper pyrophosphate. of mantoquita or CuSO of the main salt of electroplate liquid4。
Also containing the complexant for electroplating that concentration is 0.1～2mol/L in the electroplate liquid A；The complexant for electroplating is burnt phosphorus Any one in hydrochlorate, sulphuric acid, sulfate, citrate, triethanolamine or combination.As the pyrophosphate of complexant for electroplating It is preferred that potassium pyrophosphate.
Also contain doped chemical in the electroplate liquid A, the doped chemical be antimony, germanium, lead, aluminum, zinc, silver, cobalt, ferrum, manganese, Any one in chromium, molybdenum, titanium, zirconium or its combination；The doped chemical is 0.5～5 with the mol ratio of the main salt of electroplate liquid：100. Doped chemical is added in electrolyte in the form of ion (salt).
In the electroplate liquid B, the content of additive is 0.5～10g/L；The additive is sodium polydithio-dipropyl sulfonate (SP), thiourea, triethanolamine, polyether polyol, Polyethylene Glycol (PEG), polypropylene glycol (PPG), gelatin, glucose, 3- sulfydryls- Any one in 1- propanesulfonates (MPS) or its combination.
Step 3) described in faying face isolated chromatography layer process be that cathode surface shape is sprayed on using hydroxybenzotriazole (HOBT) Into combination interface isolated chromatography layer；The thickness of the combination interface isolated chromatography layer is 10～50nm.
Negative electrode used by the plating is cathode roll, and it is glass carbon, high pyrolytic graphite, proof gold in order that the cathode roll is material The roll electrode of category ruthenium, ruthenium-base alloy or pure titanium；Anode used by the plating be positive plate, the positive plate be tin electrode, Any one in copper electrode or two kinds.
Step 4) described in plating for constant current plating or pulse current plating, electric current density be 0.5～20A/dm2, electricity The plating time is 10～30min, and electroplating temperature is 25～65 DEG C.
Step 5) described in post processing be the thick plate of alloy is carried out successively extruding solidification, surface passivation, epoxy silane oxidation Process.
The pressure of the extruding solidification is 3～6MPa.The surface passivation blows soon surface passivation for 60 DEG C of hot blasts.
Step 5) in gained tin base alloy anode plate thickness be 20～200 μm.
A kind of lithium ion battery preparation method of tin base alloy anode plate, comprises the following steps：
1) the main salt of power taking plating solution, prepare containing tin ion concentration be 0.05～0.5mol/L, copper ion concentration be 0.06～ The electroplate liquid A of 0.6mol/L；
2) additive is added in electroplate liquid A, obtains electroplate liquid B；
3) negative electrode used to plating is combined face isolated chromatography layer and processes, and makes cathode surface form combination interface isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, in cathode surface the thick plate of alloy is formed；
5) the thick plate of alloy is carried out into post processing from after cathode surface stripping, obtains final product tin base alloy anode plate.
The lithium ion battery tin base alloy anode plate of the present invention, to plating, negative electrode used is combined at the isolated chromatography layer of face Reason, makes cathode surface form combination interface isolated chromatography layer, then prepares kamash alloy using the method one-step shaping of electro-deposition (plating) Negative plate, it is easy to peel off from negative terminal surface；Gained tin base alloy anode plate takes into account active substance and collector is integrated, and eliminates Traditional collector, with high-energy-density and high volume density, solves during charge and discharge cycles active substance from afflux The problem come off on body.
The lithium ion battery of the present invention preparation method of tin base alloy anode plate, step 1) by controlling electroplate liquid in it is main Salt copper and tin ratio, and then the alloying component of controlling plate；The species and content of doped chemical in by adjusting electroplate liquid, control is closed Its corresponding metal-doped amount in golden plate.Step 3) in, combination interface isolated chromatography layer is peeled off beneficial to alloy material from cathode roll, together When certain antisepsises are played to the alloy material after peeling.Plate selects any one in tin electrode, copper electrode Or two kinds, one or two the supply in electrolyte copper, tin ion is given by positive plate.Step 4) in, during plating, pass through Adjust depositing current density control metallic plate formation speed and plate body thickness.Step 5) in, at the later stage to the thick plate of alloy Reason, meets application requirement.The preparation method gained kamash alloy of the present invention is mainly with Cu6Sn5Based on, while also there are other Alloying component, such as Cu3Sn, CuSn etc..
The lithium ion battery of the present invention preparation method of tin base alloy anode plate, is combined to the negative electrode used by plating Face isolated chromatography layer is processed, and makes cathode surface form combination interface isolated chromatography layer, then using the method one-step shaping system of electro-deposition (plating) Standby tin base alloy anode plate, it is easy to peel off from negative terminal surface；Gained tin base alloy anode plate takes into account active substance and collector is Integrally, traditional collector is eliminated, with high-energy-density and high volume density, activity during charge and discharge cycles is solved The problem that material comes off from collector；Preparation process is simple, easy to operate, cost-effective, time saving and energy saving, operability compared with By force, it is adapted to large-scale industrial production.
Description of the drawings
Fig. 1 is the plating schematic diagram of the preparation method of the lithium ion battery tin base alloy anode plate of embodiment 1；
Fig. 2 is the x-ray diffraction pattern of the gained tin base alloy anode plate of embodiment 1；
Fig. 3 is the energy spectrum diagram of the gained tin base alloy anode plate of embodiment 1；
Fig. 4 is the cycle performance schematic diagram of the half-cell prepared using the gained tin base alloy anode plate of embodiment 1.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The lithium ion battery of the present embodiment tin base alloy anode plate, is prepared by following methods：
1) the main salt of power taking plating solution and complexant for electroplating prepare electroplate liquid, and in the electroplate liquid, the concentration of potassium pyrophosphate is 0.1mol/L, the concentration of Copper pyrophosphate. is 0.06mol/L, and the concentration of ditin diphosphate is 0.05mol/L；By the plating for having configured Liquid is staticly settled, and is filtrated to get transparent copper and tin solution, as electroplate liquid A.
2) SP, PEG, gelatin are separately added into as additive in electroplate liquid A, obtain electroplate liquid B, SP in the electroplate liquid B, PEG, the total content of gelatin are 0.5g/L；
3) from pure titanium roller as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode, and to plating, negative electrode used adopts hydroxyl Base benzotriazole is combined face isolated chromatography layer and processes, and makes cathode surface form hydroxybenzotriazole combination interface of the thickness for 10nm Isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, plating schematic diagram is as shown in figure 1, the radian pair with cathode roll 1 In the anode 2 answered and the corresponding part of cathode roll 1 immersion electrolyte, signal bronze is deposited on cathode roll 1, with the rotation of cathode roll Leave electrolyte and the thick plate 3 of alloy is peeled off to obtain from cathode roll 1；The plating is constant current plating, and electric current density is 1A/dm2, Electroplating temperature is 25 DEG C, and holding electroplating bath components are constant during electro-deposition (plating), and electroplating time is 30min, in negative electrode table It is Cu that face forms main component6Sn5The thick plate of alloy；
5) by the thick plate of alloy from after cathode surface stripping, extruding solidification is carried out successively, under the conditions of 60 DEG C surface passivation and Epoxy silane oxidation processes, obtain final product the tin base alloy anode plate that thickness is 20 μm.
X-ray (XRD) analysis and power spectrum (EDS) analysis are carried out to the tin base alloy anode plate obtained by the present embodiment, as a result As shown in Figure 2,3.The XRD of Fig. 2 shows and generates Cu6Sn5Alloy；The EDS of Fig. 3 shows Cu：Sn ratios substantially conform to 6:5.
Using the present embodiment gained tin base alloy anode plate assembling half-cell：Using gained tin base alloy anode plate as work Electrode (positive pole), used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF for lithium piece6(volume ratio EC：DEC= 1:1) as electrolyte, under argon atmosphere, 2032 type half-cells are prepared in glove box.
The battery is tested with blue electricity battery system, as a result as shown in Figure 4.Under 200mA/g electric currents, 0-2V voltages, just Beginning capacity is 992.3mAh/g, and capacity remains as 506.2mAh/g after 100 circulations.
Embodiment 2
The lithium ion battery of the present embodiment tin base alloy anode plate, is prepared by following methods：
1) the main salt of power taking plating solution and complexant for electroplating prepare electroplate liquid, and in the electroplate liquid, the concentration of potassium pyrophosphate is 0.5mol/L, the concentration of Copper pyrophosphate. is 0.3mol/L, and the concentration of ditin diphosphate is 0.25mol/L, the concentration of ferric phrophosphate For 0.02mol/L；The electroplate liquid for having configured is staticly settled, transparent copper and tin solution, as electroplate liquid A is filtrated to get.
2) SP, PEG, gelatin are separately added into as additive in electroplate liquid A, obtain electroplate liquid B, SP in the electroplate liquid B, PEG, the total content of gelatin are 5g/L；
3) from pure titanium roller as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode, and to plating, negative electrode used adopts hydroxyl Base benzotriazole is combined face isolated chromatography layer and processes, and makes cathode surface form hydroxybenzotriazole combination interface of the thickness for 20nm Isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, the plating is constant current plating, and electric current density is 5A/ dm2, electroplating temperature is 30 DEG C, and during electro-deposition (plating) F is kepte 3+Concentration is constant, electroplating bath components are constant, electroplating time For 10min, it is Cu to form main component in cathode surface6Sn5The thick plate of alloy；
5) by the thick plate of alloy from after cathode surface stripping, extruding solidification is carried out successively, under the conditions of 60 DEG C surface passivation and Epoxy silane oxidation processes, obtain final product the tin base alloy anode plate that thickness is 100 μm.
Using the present embodiment gained tin base alloy anode plate assembling half-cell：Using gained tin base alloy anode plate as work Electrode (positive pole), used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF for lithium piece6(volume ratio EC：DEC= 1:1) as electrolyte, under argon atmosphere, 2032 type half-cells are prepared in glove box.
The battery is tested with blue electricity battery system, under 200mA/g electric currents, 0-2V voltages, initial capacity is 985.8mAh/g, capacity remains as 470.6mAh/g after 100 circulations.
Embodiment 3
The lithium ion battery of the present embodiment tin base alloy anode plate, is prepared by following methods：
1) the main salt of power taking plating solution and complexant for electroplating prepare electroplate liquid, and in the electroplate liquid, the concentration of potassium pyrophosphate is 0.5mol/L, the concentration of Copper pyrophosphate. is 0.15mol/L, and the concentration of ditin diphosphate is 0.125mol/L, Cr3+Concentration be 0.01mol/L；The electroplate liquid for having configured is staticly settled, transparent copper and tin solution, as electroplate liquid A is filtrated to get.
2) SP, PEG, gelatin are separately added into as additive in electroplate liquid A, obtain electroplate liquid B, SP in the electroplate liquid B, PEG, the total content of gelatin are 5g/L；
3) from pure titanium roller as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode, and to plating, negative electrode used adopts hydroxyl Base benzotriazole is combined face isolated chromatography layer and processes, and makes cathode surface form hydroxybenzotriazole combination interface of the thickness for 30nm Isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, the plating is constant current plating, and electric current density is 10A/ dm2, electroplating temperature is 45 DEG C, and during electro-deposition (plating) Cr is kept3+Concentration is constant, electroplating bath components are constant, electroplating time For 10min, it is Cu to form main component in cathode surface6Sn5The thick plate of alloy；
5) by the thick plate of alloy from after cathode surface stripping, extruding solidification is carried out successively, under the conditions of 60 DEG C surface passivation and Epoxy silane oxidation processes, obtain final product the tin base alloy anode plate that thickness is 60 μm.
Using the present embodiment gained tin base alloy anode plate assembling half-cell：Using gained tin base alloy anode plate as work Electrode (positive pole), used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF for lithium piece6(volume ratio EC：DEC= 1:1) as electrolyte, under argon atmosphere, 2032 type half-cells are prepared in glove box.
The battery is tested with blue electricity battery system, under 200mA/g electric currents, 0-2V voltages, initial capacity is 980.4mAh/g, capacity remains as 482.9mAh/g after 100 circulations.
Embodiment 4
The lithium ion battery of the present embodiment tin base alloy anode plate, is prepared by following methods：
1) the main salt of power taking plating solution and complexant for electroplating prepare electroplate liquid, in the electroplate liquid, CuSO4Concentration be 0.12mol/L, SnSO4Concentration be 0.15mol/L, H2SO4Concentration be 1mol/L, the concentration of AgCl is 0.01mol/L；Will The electroplate liquid for having configured is staticly settled, and is filtrated to get transparent copper and tin solution, as electroplate liquid A.
2) PEG, gelatin, glucose and polyether polyol are separately added into as additive in electroplate liquid A, obtain electroplate liquid B, PEG, gelatin, the total content of glucose are 5g/L in the electroplate liquid B, and the concentration of polyether polyol is 4g/L；
3) from high order graphite roller as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode, and to plating, negative electrode used is adopted Face isolated chromatography layer is combined with hydroxybenzotriazole to process, make cathode surface form the hydroxybenzotriazole that thickness is 20nm and combine Interface isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, the plating is constant current plating, and electric current density is 3A/ dm2, electroplating temperature is 50 DEG C, and during electro-deposition (plating) Ag is kept+Concentration is constant, electroplating bath components are constant, and electroplating time is 10min, it is Cu to form main component in cathode surface6Sn5The thick plate of alloy；
5) by the thick plate of alloy from after cathode surface stripping, extruding solidification is carried out successively, under the conditions of 60 DEG C surface passivation and Epoxy silane oxidation processes, obtain final product the tin base alloy anode plate that thickness is 40 μm.
Using the present embodiment gained tin base alloy anode plate assembling half-cell：Using gained tin base alloy anode plate as work Electrode (positive pole), used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF for lithium piece6(volume ratio EC：DEC= 1:1) as electrolyte, under argon atmosphere, 2032 type half-cells are prepared in glove box.
The battery is tested with blue electricity battery system, under 200mA/g electric currents, 0-2V voltages, initial capacity is 979.6mAh/g, capacity remains as 488.8mAh/g after 100 circulations.
Embodiment 5
The lithium ion battery of the present embodiment tin base alloy anode plate, is prepared by following methods：
1) the main salt of power taking plating solution and complexant for electroplating prepare electroplate liquid, in the electroplate liquid, CuSO4Concentration be 0.6mol/L, SnSO4Concentration be 0.5mol/L, H2SO4Concentration be 2mol/L, AlCl3Concentration be 0.006mol/L；Will The electroplate liquid for having configured is staticly settled, and is filtrated to get transparent copper and tin solution, as electroplate liquid A.
2) thiourea, PEG, gelatin, glucose and polyether polyol are separately added into as additive in electroplate liquid A, obtain electric Plating solution B, thiourea, PEG, gelatin, the total content of glucose are 2g/L in the electroplate liquid B, and the concentration of polyether polyol is 8g/L；
3) from high purity titanium roller as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode, and plating negative electrode used is adopted Hydroxybenzotriazole is combined face isolated chromatography layer and processes, and makes cathode surface form thickness and combines boundary for the hydroxybenzotriazole of 50nm Face isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, it is described plating be pulse current plating, electric current density be 1～ 20A/dm2, electroplating temperature is 65 DEG C, and during electro-deposition (plating) Al is kept3+Concentration is constant, electroplating bath components are constant, plating Time is 30min, and it is Cu to form main component in cathode surface6Sn5The thick plate of alloy；
5) by the thick plate of alloy from after cathode surface stripping, extruding solidification is carried out successively, under the conditions of 60 DEG C surface passivation and Epoxy silane oxidation processes, obtain final product the tin base alloy anode plate that thickness is 200 μm.
Using the present embodiment gained tin base alloy anode plate assembling half-cell：Using gained tin base alloy anode plate as work Electrode (positive pole), used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF for lithium piece6(volume ratio EC：DEC= 1:1) as electrolyte, under argon atmosphere, 2032 type half-cells are prepared in glove box.
The battery is tested with blue electricity battery system, under 200mA/g electric currents, 0-2V voltages, initial capacity is 982.1mAh/g, capacity remains as 532.4mAh/g after 100 circulations.
Embodiment 6
The lithium ion battery of the present embodiment tin base alloy anode plate, is prepared by following methods：
1) the main salt of power taking plating solution and complexant for electroplating prepare electroplate liquid, in the electroplate liquid, CuSO4Concentration be 0.3mol/L, SnSO4Concentration be 0.3mol/L, H2SO4Concentration be 1mol/L, AlCl3Concentration be 0.02mol/L；To match somebody with somebody The electroplate liquid put is staticly settled, and is filtrated to get transparent copper and tin solution, as electroplate liquid A.
2) PEG, gelatin, glucose and triethanolamine, polyether polyol are separately added into as additive in electroplate liquid A, Electroplate liquid B, PEG in the electroplate liquid B, gelatin, the total content of glucose are 5g/L, triethanolamine, polyether polyol it is total Concentration is 5g/L；
3) from glass carbon roller as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode, and to plating, negative electrode used adopts hydroxyl Base benzotriazole is combined face isolated chromatography layer and processes, and makes cathode surface form hydroxybenzotriazole combination interface of the thickness for 50nm Isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, the plating is pulse current plating, and electric current density is 0.5 ～15A/dm2, electroplating temperature is 25 DEG C, and during electro-deposition (plating) Al is kept3+Concentration is constant, electroplating bath components are constant, electricity The plating time is 20min, and it is Cu to form main component in cathode surface6Sn5The thick plate of alloy；
5) by the thick plate of alloy from after cathode surface stripping, extruding solidification is carried out successively, under the conditions of 60 DEG C surface passivation and Epoxy silane oxidation processes, obtain final product the tin base alloy anode plate that thickness is 150 μm.
Using the present embodiment gained tin base alloy anode plate assembling half-cell：Using gained tin base alloy anode plate as work Electrode (positive pole), used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF for lithium piece6(volume ratio EC：DEC= 1:1) as electrolyte, under argon atmosphere, 2032 type half-cells are prepared in glove box.
The battery is tested with blue electricity battery system, under 200mA/g electric currents, 0-2V voltages, initial capacity is 991.9mAh/g, capacity remains as 514.7mAh/g after 100 circulations.
Embodiment 7
The lithium ion battery of the present embodiment tin base alloy anode plate, is prepared by following methods：
1) the main salt of power taking plating solution and complexant for electroplating prepare electroplate liquid, in the electroplate liquid, CuSO4Concentration be 0.12mol/L, SnSO4Concentration be 0.15mol/L, H2SO4Concentration be 1mol/L, the concentration of ammonium citrate is 0.5mol/L, The concentration of ammonium sulfate is 0.5mol/L；The electroplate liquid for having configured is staticly settled, transparent copper and tin solution is filtrated to get, as electricity Plating solution A.
2) PEG, PPG, gelatin, MPS are separately added into as additive in electroplate liquid A, obtain electroplate liquid B, the electroplate liquid B Middle PEG, PPG, gelatin, the total content of MPS are 4g/L；
3) from metal Ru roller as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode, and plating negative electrode used is adopted Hydroxybenzotriazole is combined face isolated chromatography layer and processes, and makes cathode surface form thickness and combines boundary for the hydroxybenzotriazole of 20nm Face isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, the plating is constant current plating, and electric current density is 10A/ dm2, electroplating temperature is 25 DEG C, keeps that main salt ionic concentration is constant, electroplating bath components are constant during electro-deposition (plating), is electroplated Time is 30min, and it is Cu to form main component in cathode surface6Sn5The thick plate of alloy；
5) by the thick plate of alloy from after cathode surface stripping, extruding solidification is carried out successively, under the conditions of 60 DEG C surface passivation and Epoxy silane oxidation processes, obtain final product the tin base alloy anode plate that thickness is 120 μm.
Using the present embodiment gained tin base alloy anode plate assembling half-cell：Using gained tin base alloy anode plate as work Electrode (positive pole), used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF for lithium piece6(volume ratio EC：DEC= 1:1) as electrolyte, under argon atmosphere, 2032 type half-cells are prepared in glove box.
The battery is tested with blue electricity battery system, under 200mA/g electric currents, 0-2V voltages, initial capacity is 987.7mAh/g, capacity remains as 496.2mAh/g after 100 circulations.
Embodiment 8
The lithium ion battery of the present embodiment tin base alloy anode plate, is prepared by following methods：
1) the main salt of power taking plating solution and complexant for electroplating prepare electroplate liquid, in the electroplate liquid, CuSO4Concentration be 0.12mol/L, SnSO4Concentration be 0.15mol/L, ZnSO4Concentration be 0.03mol/L, H2SO4Concentration be 1mol/L, lemon The concentration of lemon acid ammonium is 0.5mol/L, and the concentration of ammonium sulfate is 0.5mol/L；The electroplate liquid for having configured is staticly settled, is filtered To transparent copper and tin solution, as electroplate liquid A.
2) PEG, PPG, gelatin, MPS are separately added into as additive in electroplate liquid A, obtain electroplate liquid B, the electroplate liquid B Middle PEG, PPG, gelatin, the total content of MPS are 1g/L；
3) from metal Ru roller as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode, and plating negative electrode used is adopted Hydroxybenzotriazole is combined face isolated chromatography layer and processes, and makes cathode surface form thickness and combines boundary for the hydroxybenzotriazole of 20nm Face isolated chromatography layer；
4) electroplate liquid B is put in electroplating bath and is electroplated, the plating is constant current plating, and electric current density is 15A/ dm2, electroplating temperature is 25 DEG C, and during electro-deposition (plating) Zn is kept2+Concentration is constant, electroplating bath components are constant, electroplating time For 15min, it is Cu to form main component in cathode surface6Sn5The thick plate of alloy；
5) by the thick plate of alloy from after cathode surface stripping, extruding solidification is carried out successively, under the conditions of 60 DEG C surface passivation and Epoxy silane oxidation processes, obtain final product the tin base alloy anode plate that thickness is 80 μm.
Using the present embodiment gained tin base alloy anode plate assembling half-cell：Using gained tin base alloy anode plate as work Electrode (positive pole), used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF for lithium piece6(volume ratio EC：DEC= 1:1) as electrolyte, under argon atmosphere, 2032 type half-cells are prepared in glove box.
The battery is tested with blue electricity battery system, under 200mA/g electric currents, 0-2V voltages, initial capacity is 992.6mAh/g, capacity remains as 537.1mAh/g after 100 circulations.
Comparative example 1
The negative plate of this comparative example, is prepared by following methods：
1) it is collector from Copper Foil, to collector oil removing, except oxide；
1) electroplate liquid is prepared, in the electroplate liquid, the concentration of potassium pyrophosphate is 0.1mol/L, and the concentration of Copper pyrophosphate. is 0.06mol/L, the concentration of ditin diphosphate is 0.05mol/L；The electroplate liquid for having configured is staticly settled, is filtrated to get transparent Copper and tin solution, as electroplate liquid A.
2) SP, PEG, gelatin are separately added into as additive in electroplate liquid A, obtain electroplate liquid B, added in the electroplate liquid B Plus the total content of agent is 0.5g/L；
3) from Copper Foil as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode；
4) electroplate liquid B is put in electroplating bath and is electroplated, the plating is constant current plating, and electric current density is 5A/ dm2, electroplating temperature is 25 DEG C, and holding electroplating bath components are constant during electro-deposition (plating), and electroplating time is 30min；
5) alloy sheets obtained by electro-deposition are dried under the conditions of 60 DEG C, that is, are able to the negative plate that Copper Foil is collector.
Using this comparative example gained negative plate assembling half-cell：Using gained negative plate as working electrode (positive pole), lithium piece Used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF6(volume ratio EC：DEC=1:1) as electrolyte, Under argon atmosphere, 2032 type half-cells are prepared in glove box.
Comparative example 2
The negative plate of this comparative example, is prepared by following methods：
1) it is collector from foam copper band, to collector oil removing, except oxide；
1) electroplate liquid is prepared, in the electroplate liquid, the concentration of potassium pyrophosphate is 0.1mol/L, and the concentration of Copper pyrophosphate. is 0.06mol/L, the concentration of ditin diphosphate is 0.05mol/L；The electroplate liquid for having configured is staticly settled, is filtrated to get transparent Copper and tin solution, as electroplate liquid A.
2) SP, PEG, gelatin are separately added into as additive in electroplate liquid A, obtain electroplate liquid B, added in the electroplate liquid B Plus the total content of agent is 0.5g/L；
3) from Copper Foil as negative electrode, stannum copper ratio be 5:6 battery lead plate is anode；
4) electroplate liquid B is put in electroplating bath and is electroplated, the plating is constant current plating, and electric current density is 5A/ dm2, electroplating temperature is 25 DEG C, and holding electroplating bath components are constant during electro-deposition (plating), and electroplating time is 30min；
5) alloy sheets obtained by electro-deposition are dried under the conditions of 60 DEG C, that is, are able to the negative pole that foam copper band is collector Plate.
Using this comparative example gained negative plate assembling half-cell：Using gained negative plate as working electrode (positive pole), lithium piece Used as auxiliary electrode (negative pole), Celgard2400 is used as barrier film, 1M LiPF6(volume ratio EC：DEC=1:1) as electrolyte, Under argon atmosphere, 2032 type half-cells are prepared in glove box.
Experimental example 1
The electrical property of the half-cell that this experimental example is prepared to embodiment 1-8, comparative example 1, the gained negative plate of comparative example 2 is carried out Test.Method of testing：With blue electricity battery system test battery, under 200mA/g electric currents, 0-2V voltages, following for battery is tested Ring performance.As a result it is as shown in table 1.
Half-cell charge-discharge performance prepared by the Different electrodes of table 1 compares (unit：mAh/g)
Cycle-index 1 20 40 60 80 100
Embodiment 1 992.3 730.7 700.3 565.6 538.4 506.2
Embodiment 2 985.8 731.3 709.1 606.5 517.4 470.6
Embodiment 3 980.4 792.1 718.6 657.4 563.1 482.9
Embodiment 4 979.6 812.7 731.5 671.1 552.9 488.8
Embodiment 5 982.1 731.6 699.8 619.1 562.3 532.4
Embodiment 6 991.9 729.5 682.9 578.4 562.1 514.7
Embodiment 7 987.7 746.7 681.9 593.6 543.1 496.2
Embodiment 8 992.6 756.2 684.2 607.4 575.9 537.1
Comparative example 1 993.2 791.2 689 478.9 394.6 321.8
Comparative example 2 993.4 864.1 706.4 494.7 376.3 336.7
As it can be seen from table 1 the half-cell prepared using embodiment 1-8 gained negative plate in charge and discharge cycles 100 times Afterwards, its capacity is still 500mAh/g or so, the significantly larger than capacity (below 340mAh/g) of comparative example.Test result indicate that, adopt The battery prepared with the negative plate of the present invention, with excellent cycle performance.

Claims (7)

1. a kind of lithium ion battery tin base alloy anode plate, it is characterised in that：The tin base alloy anode plate is by following methods Prepare：
1) the main salt of power taking plating solution, it is 0.06～0.6mol/ that preparation contains tin ion concentration for 0.05～0.5mol/L, copper ion concentration The electroplate liquid A of L；
2) additive is added in electroplate liquid A, obtains electroplate liquid B；
3) negative electrode used to plating is combined face isolated chromatography layer and processes, and makes cathode surface form combination interface isolated chromatography layer；It is described The process of faying face isolated chromatography layer is to be sprayed on cathode surface using hydroxybenzotriazole to form combination interface isolated chromatography layer；Combination circle The thickness of face isolated chromatography layer is 10～50nm；
Negative electrode used by the plating is cathode roll, and it is glass carbon, high pyrolytic graphite, simple metal in order that the cathode roll is material The roll electrode of ruthenium, ruthenium-base alloy or pure titanium；Anode used by the plating is positive plate, and the positive plate is tin electrode, copper Any one in electrode or two kinds；
4) electroplate liquid B is put in electroplating bath and is electroplated, in cathode surface the thick plate of alloy is formed；
5) the thick plate of alloy is carried out into post processing from after cathode surface stripping, obtains final product main component for Cu6Sn5Tin base alloy anode Plate；The post processing is to carry out extruding solidification, surface passivation, epoxy silane oxidation processes successively to the thick plate of alloy.
2. lithium ion battery according to claim 1 tin base alloy anode plate, it is characterised in that：In the electroplate liquid A Also containing the complexant for electroplating that concentration is 0.1～2mol/L；The complexant for electroplating is pyrophosphate, sulphuric acid, sulfate, Fructus Citri Limoniae Any one in hydrochlorate, triethanolamine or combination.
3. lithium ion battery according to claim 1 tin base alloy anode plate, it is characterised in that：In the electroplate liquid A Also contain doped chemical, the doped chemical is any one in antimony, germanium, lead, aluminum, zinc, silver, cobalt, ferrum, manganese, chromium, molybdenum, titanium, zirconium Plant or its combination；The doped chemical is 0.5～5 with the mol ratio of the main salt of electroplate liquid：100.
4. lithium ion battery according to claim 1 tin base alloy anode plate, it is characterised in that：In the electroplate liquid B, The content of additive is 0.5～10g/L；The additive is that sodium polydithio-dipropyl sulfonate, thiourea, triethanolamine, polyethers are more Any one in first alcohol, Polyethylene Glycol, polypropylene glycol, gelatin, glucose, 3- sulfydryl -1- propanesulfonates or its combination.
5. lithium ion battery according to claim 1 tin base alloy anode plate, it is characterised in that：Step 4) described in electricity It is that constant current plating or pulse current are electroplated to plate, and electric current density is 0.5～20A/dm2, electroplating time is 10～30min, is electroplated Temperature is 25～65 DEG C.
6. lithium ion battery according to claim 1 tin base alloy anode plate, it is characterised in that：Step 5) middle gained stannum The thickness of based alloy negative plate is 20～200 μm.
7. a kind of lithium ion battery preparation method of tin base alloy anode plate, it is characterised in that：Comprise the following steps：
1) the main salt of power taking plating solution, it is 0.06～0.6mol/ that preparation contains tin ion concentration for 0.05～0.5mol/L, copper ion concentration The electroplate liquid A of L；
2) additive is added in electroplate liquid A, obtains electroplate liquid B；
3) negative electrode used to plating is combined face isolated chromatography layer and processes, and makes cathode surface form combination interface isolated chromatography layer；It is described The process of faying face isolated chromatography layer is to be sprayed on cathode surface using hydroxybenzotriazole to form combination interface isolated chromatography layer；Combination circle The thickness of face isolated chromatography layer is 10～50nm；
Negative electrode used by the plating is cathode roll, and it is glass carbon, high pyrolytic graphite, simple metal in order that the cathode roll is material The roll electrode of ruthenium, ruthenium-base alloy or pure titanium；Anode used by the plating is positive plate, and the positive plate is tin electrode, copper Any one in electrode or two kinds；
4) electroplate liquid B is put in electroplating bath and is electroplated, in cathode surface the thick plate of alloy is formed；
5) the thick plate of alloy is carried out into post processing from after cathode surface stripping, obtains final product main component for Cu6Sn5Tin base alloy anode Plate；The post processing is to carry out extruding solidification, surface passivation, epoxy silane oxidation processes successively to the thick plate of alloy.
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