CN108987678A - A kind of preparation method containing slicker solder/graphene composite coating lead-acid battery electrode - Google Patents

A kind of preparation method containing slicker solder/graphene composite coating lead-acid battery electrode Download PDF

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CN108987678A
CN108987678A CN201810857927.5A CN201810857927A CN108987678A CN 108987678 A CN108987678 A CN 108987678A CN 201810857927 A CN201810857927 A CN 201810857927A CN 108987678 A CN108987678 A CN 108987678A
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lead
preparation
acid
composite coating
slicker solder
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CN108987678B (en
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戴长松
杨少强
李如宏
蔡先玉
杨宝峰
胡信国
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead 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

Abstract

The present invention provides a kind of preparation methods containing slicker solder/graphene composite coating lead-acid battery electrode, belong to battery terminal preparation technical field.Technical solution: firstly, being pre-processed to grid alloy matrix；Then, graphene oxide electric depositing solution is prepared；Later, using DH1718E-4 type power supply, three-electrode system is assembled, pretreated grid alloy is Electrode, and terne metal electrode is auxiliary electrode, using 10~100mA constant current, 5~60min of electro-deposition can form slicker solder/graphene composite coating on Electrode.Method of the invention is easy to operate, can be improved the electric conductivity of grid alloy Yu positive active material interface, and lead-acid accumulator cycle life under the conditions of 100% depth of discharge can reach 367 times.

Description

A kind of preparation containing slicker solder/graphene composite coating lead-acid battery electrode Method
Technical field
The invention belongs to metal Surface Treatment Technique field or battery terminal preparation technical fields, and in particular to and a kind of slicker solder/ The preparation method of the preparation method of graphene composite coating or the lead-acid battery electrode containing this kind of coating.
Background technique
For current battery industry in the case of for, lead-acid accumulator be still in secondary cell market consumption figure it is maximum A kind of battery, due to lead-acid accumulator have be not required to add sour water, without acid mist is precipitated, capacity is big, price is low, self-discharge rate is low, The advantages that compact-sized and memory-less effect, while can arbitrarily place use, convenient in carrying, using cleaning, in recent years in energy storage It is widely used in system.
In plumbic acid energy-storage battery technical field, the performance of grid and reactive species interface is most important, is directly related to The service life of battery and performance.Phase composition, thickness and the electric conductivity of grid and reactive species interface are to the discharge performance of battery and follow The ring service life plays a decisive role, and interface conductivity is poor, influences heavy-current discharge performance and charge acceptance, mentions battery life Preceding termination can't fully meet application requirement.So the chemical property at research grid interface, overcomes as caused by interface A series of problems just seems critically important.
Summary of the invention
To solve the above problems, improving plumbic acid energy-storage battery service life, it is compound that the present invention provides a kind of slicker solder/graphene The preparation method of the preparation method of coating or the lead-acid battery electrode containing this kind of coating.
Slicker solder provided by the invention/graphene composite coating preparation method sequentially includes the following steps:
1) base material pre-processes: base material successively polished, washed, oil removing, etch processing；
2) the base material immersion that step 1) is handled well slicker solder/graphene composite coating deposition: is contained into lead fluoborate, fluorine In aqueous solution, that is, electric depositing solution of boric acid stannous, fluoboric acid, boric acid, peptone and graphene, electro-deposition forms slicker solder/graphite Alkene composite coating.
Step 1) the base material is grid for lead-acid storage batteries alloy material.
The alloy material for slab lattice alloy compositions and content: Pb >=98.6wt.%, 0.07~0.11wt.%Ca, 1.0~ 1.2wt.%Sn, 0.02~0.03wt.%Al.
Step 1) the polishing specially polishes the base material time resistance to silicon carbide paper of 600#, 1000# and 2000#.
Step 1) the oil removing refers to the base material after washing impregnating oil removing at 60~80 DEG C in alkaline degreasing liquid 0.5~2.0 minute, then ultrasonic cleaning 5~15 minutes in deionized water.
Above-mentioned alkaline degreasing liquid is the aqueous solution containing 20~30g/L of 20~30g/L of sodium hydroxide and sodium carbonate.
Step 1) the etch, refers to and impregnates the base material after oil removing in etching solution 1 minute, the etching solution be containing There are the aqueous solution of 10~70mL/L of hydrogen peroxide of the hydrofluoric acid 50~500mL/L and 30wt.% of 40wt.%.
Step 2) the electric depositing solution each component concentration are as follows: 100~1000g/L of lead fluoborate, stannous fluoboric acid 10~ 80g/L, 50~400g/L of fluoboric acid, 1~15g/L of boric acid, 0.1~1.5g/L of peptone, 0.01~1g/L of graphene.
Step 2) the electro-deposition, condition are as follows: 10~100mA constant current, 5~60min of electro-deposition.
The power supply used is DH1718E-4 type power supply.
In addition, the preparation side provided by the invention containing above-mentioned slicker solder/graphene composite coating lead-acid battery electrode Method sequentially includes the following steps:
One, the pretreatment of lead acid accumulator plate grid: lead acid accumulator plate grid successively washed, oil removing, etch processing；
Two, the grid immersion that step 1 is handled well slicker solder/graphene composite coating deposition: is contained into lead fluoborate, fluorine boron In aqueous solution, that is, electric depositing solution of sour stannous, fluoboric acid, boric acid, peptone and graphene, electro-deposition, be made with slicker solder/ The grid of graphene composite coating；
Three, the preparation of lead-acid battery electrode: step 2 is prepared successive with slicker solder/graphene composite coating grid It handles, is prepared containing slicker solder/graphene composite coating lead-acid accumulator electricity by surface full-filling lead plaster and curing and drying Pole.
Grid described in step 1 is gravity casting type grid or the stretch grid, constituent material ingredient are as follows: Pb >= 98.6wt.%, 0.07~0.11wt.%Ca, 1.0~1.2wt.%Sn, 0.02~0.03wt.%Al, slab lattice thickness 2mm.
Oil removing described in step 1 refers to that the base material after washing is impregnated chemistry in alkaline degreasing liquid at 60~80 DEG C remove Oil 0.5~2.0 minute, then ultrasonic cleaning 5~15 minutes in deionized water.
Above-mentioned alkaline degreasing liquid is the aqueous solution containing 20~30g/L of 20~30g/L of sodium hydroxide and sodium carbonate.
Etch described in step 1 refers to and impregnates the base material after oil removing in etching solution 1 minute, the etching solution be containing There are the aqueous solution of 10~70mL/L of hydrogen peroxide of the hydrofluoric acid 50~500mL/L and 30wt.% of 40wt.%.
Electric depositing solution each component concentration described in step 2 are as follows: 100~1000g/L of lead fluoborate, stannous fluoboric acid 10~ 80g/L, 50~400g/L of fluoboric acid, 1~15g/L of boric acid, 0.1~1.5g/L of peptone, 0.01~1g/L of graphene.
Electro-deposition described in step 2, condition are as follows: 10~100mA constant current, 5~60min of electro-deposition.
The power supply used is DH1718E-4 type power supply.
Lead plaster described in step 3 contains lead powder, red lead, polypropylene fibre, distilled water and sulfuric acid.
In above-mentioned lead plaster, each component presses lead powder: red lead: polypropylene fibre: distilled water: sulfuric acid weight percent is 3000: 800:6:(50-150):800。
The wherein raw material specification of each component are as follows: lead powder: oxidizability 77 ± 3%, red lead: purity > 99.9992%, polypropylene Fiber: 3D × 4 (fineness 3D, length 4mm), sulfuric acid: 1.38g/cm3。
Full-filling lead plaster described in step 3, lead plaster temperature is 45 DEG C when full-filling, full-filling thickness are as follows: 2mm, full-filling lead plaster have operated Cheng Hou is dipped in the 1.14g/cm that density is3Sulfuric acid solution in, keep 3~5 seconds after take out.
Dry solidification described in step 3, specifically: the grid after full-filling lead plaster is in 72 DEG C, the condition of relative humidity > 90% Lower solidification 24 hours, it is then 36 hours dry under the conditions of 62 DEG C.
Beneficial effect
1, the present invention prepares lead-acid battery grid alloy surface slicker solder/graphene using the electric depositing solution containing graphene Composite coating.Preparation process of the present invention is to carry out at room temperature, is required reacting environment lower；Preparation process is not related to any high Energy consumption high pollution operation, environment friendly is strong, is consequently adapted to mass production；
2, slicker solder prepared by the present invention/graphene composite coating is applied to lead-acid accumulator, and it is steady to be remarkably improved its circulation Qualitative, prepared lead-acid accumulator cycle life under the conditions of 100% depth of discharge can reach 367 times；
3, the present invention introduces the stone with highly conductive characteristic during slab lattice alloy of lead-acid battery surface treatment Black alkene material, grid alloy and the electric conductivity at positive active material interface are improved；Grapheme material can absorb plumbic acid electricity The pond anode stress that volume change generates in charge and discharge process；
4, grid alloy surface slicker solder/graphene composite coating prepared by the present invention, cost is relatively low, grasps in reaction process Make simple, material preparation method repeatability height.
Detailed description of the invention:
Fig. 1 is slicker solder/graphene composite coating SEM figure prepared by embodiment 1；
Fig. 2 is slicker solder/graphene composite coating SEM figure prepared by embodiment 2；
Fig. 3 is experimental cell cycle life test curve prepared by embodiment 3；
Fig. 4 is experimental cell cycle life test curve prepared by embodiment 4.
Specific embodiment:
Embodiment 1: slicker solder/graphene composite coating preparation
Present embodiment slicker solder/graphene composite coating preparation method and applications sequentially include the following steps:
The preparation of grid alloy sample
By grid alloy (Pb >=98.6wt.%, 0.07~0.11wt.%Ca, 1.0~1.2wt.%Sn, 0.02~ 0.03wt.%Al) being cut into floor space is 10 × 10mm2, the cube alloy block of thickness about 5mm.
The pretreatment of grid alloy sample
Grid alloy is successively used the resistance to silicon carbide paper of 600#, 1000# and 2000# polish, wash step by step, is then removed in alkalinity Oil removing 1 minute at 70 DEG C in oil liquid, then ultrasonic cleaning 10 minutes in deionized water, are finally soaking above-mentioned alloy sample It is impregnated 1 minute in erosion liquid；The alkaline degreasing formula of liquid are as follows: sodium hydroxide 25g/L, sodium carbonate 25g/L；Etch formula of liquid are as follows: Hydrofluoric acid (40wt.%) 250mL/L, hydrogen peroxide (30wt.%) 45mL/L.
The preparation of slicker solder/graphene electric depositing solution
Boric acid aqueous solution is configured first, then successively by lead fluoborate aqueous solution (50wt.%), stannous fluoboric acid aqueous solution (50wt.%), fluoborate aqueous solution (50wt.%) are added in configured boric acid aqueous solution, are finally added into above-mentioned solution Graphene is added after mixing in peptone, and ultrasonic wave disperses 20 minutes；The slicker solder/graphene electric depositing solution formula Are as follows: lead fluoborate 750g/L, stannous fluoboric acid 50g/L, fluoboric acid 300g/L, boric acid 5g/L, peptone 0.5g/L, graphene 0.05g/L。
The preparation of slicker solder/graphene composite coating
Grid alloy after pretreatment is Electrode, and terne metal electrode is auxiliary electrode, by Electrode and auxiliary It helps electrode to immerse in the electric depositing solution of preparation, the cathode and anode of DH1718E-4 type constant voltage source is separately connected, using 50mA Constant current, electro-deposition 15min can form slicker solder/graphene composite coating on the electrode.Fig. 1 is lead prepared by embodiment 1 Tin/graphene composite coating SEM figure；It will be seen from figure 1 that the partial size of grapheme material is between 10~20 μm, and uniformly It is supported in slicker solder coating.
Embodiment 2: slicker solder/graphene composite coating preparation
The difference from embodiment 1 is that: in slicker solder/graphene electric depositing solution preparation step, in the electrodeposit liquid Graphene content is 0.1g/L.Fig. 2 is slicker solder/graphene composite coating SEM figure prepared by embodiment 2；It can from Fig. 2 Out, the partial size of grapheme material is between 10~20 μm, and uniform load is in slicker solder coating.
Embodiment 3: the preparation containing slicker solder/graphene composite coating lead-acid battery electrode
The pretreatment of lead acid accumulator plate grid
Take lead acid accumulator plate grid (gravity grid casting, component Pb >=98.6wt.%, 0.07~0.11wt.%Ca, 1.0 ~1.2wt.%Sn, 0.02~0.03wt.%Al, having a size of 138mm × 66mm × 2mm) washing, then in alkaline degreasing liquid Oil removing 1 minute at 70 DEG C, then ultrasonic cleaning 10 minutes in deionized water, finally by above-mentioned alloy sample in etching solution It impregnates 1 minute；The alkaline degreasing formula of liquid are as follows: sodium hydroxide 25g/L, sodium carbonate 25g/L；Etch formula of liquid are as follows: hydrofluoric acid (40wt.%) 250mL/L, hydrogen peroxide (30wt.%) 45mL/L.
The preparation of slicker solder/graphene electric depositing solution
Boric acid aqueous solution is configured first, then successively by lead fluoborate aqueous solution (50wt.%), stannous fluoboric acid aqueous solution (50wt.%), fluoborate aqueous solution (50wt.%) are added in configured boric acid aqueous solution, are finally added into above-mentioned solution Graphene is added after mixing in peptone, and ultrasonic wave disperses 20 minutes；The slicker solder/graphene electric depositing solution formula Are as follows: lead fluoborate 750g/L, stannous fluoboric acid 50g/L, fluoboric acid 300g/L, boric acid 5g/L, peptone 0.5g/L, graphene 0.05g/L。
Slicker solder/graphene composite coating deposition
The grid pre-processed is immersed in the electric depositing solution of preparation, is separately connected DH1718E-4 type constant voltage source Cathode and anode, using 50mA constant current, electro-deposition 15min can form slicker solder/graphene composite coating on grid.
The preparation of lead-acid battery electrode
Preparation with slicker solder/graphene composite coating grid successively by surface full-filling lead plaster and curing and drying at Reason, is prepared containing slicker solder/graphene composite coating lead-acid battery electrode:
Lead paste formula
Lead plaster temperature is 45 DEG C when full-filling, full-filling thickness are as follows: 2mm.
Pickling:
After the completion of grid full-filling lead plaster, pole plate is immersed in the 1.14g/cm that density is immediately3Sulfuric acid solution in, protect It is taken out after holding 3~5 seconds.
Solidification and drying:
Solidify under conditions of 72 DEG C, relative humidity > 90% 24 hours, it is then 36 hours dry under the conditions of 62 DEG C.
It is made containing slicker solder/graphene composite coating lead-acid battery electrode, slicker solder/graphene of the electrode surface is multiple It is identical as coating prepared by embodiment 1 to close coating.
Embodiment 4: the preparation containing slicker solder/graphene composite coating lead-acid battery electrode
Difference with embodiment 3 is: in slicker solder/graphene electric depositing solution preparation step, the electric depositing solution Middle graphene content is 0.05g/L.The coating phase that the slicker solder on the electrode obtained surface/graphene composite coating is prepared with embodiment 2 Together.
5 electrode of embodiment (slicker solder/graphene composite coating) performance detection
Contain slicker solder/graphene composite coating lead-acid battery electrode as anode for prepared by embodiment 3,4 Performance detection is carried out respectively, takes negative electrode grid (gravity grid casting, component: Pb >=99.6wt.%, 0.08~0.11wt.% Ca, 0.18~0.25wt.%Sn, 0.02~0.03wt.%Al) it is used as cell negative electrode material, cathode size and positive specification phase Together, battery cathode is made through painting cream same as Example 3, curing and drying operation, difference is cathode lead plaster formula are as follows:
Cathode lead plaster formula
Experimental cell is by an anode and two cathode groups: above-mentioned battery plus-negative plate plate separated with fibreglass diaphragm, By it is negative, positive, between negative, the mode assembled battery that tab is opposite through formation process be prepared into 2V 4Ah single battery.Plates polarizing At technique:
The test of experimental cell cycle life
The test of experimental cell cycle life is completed using μ C-CF30 type battery test system, and test temperature is 25 DEG C, Depth of discharge is 100%DoD, and specific testing procedure is as follows:
Electric discharge: 0.2C is discharged to 1.8V；
Charging: 0.15C charges to 2.35V, then constant-voltage charge 4h under 2.35V；
Between upon discharging≤3h when, the cycle life EOT end of test.
Fig. 3 is the experimental cell cycle life test curve that the electrode obtained using embodiment 3 is prepared as anode；Grid Lead-acid battery cycle life reaches 367 times after alloy surface deposition slicker solder/graphene composite coating.
Fig. 4 is the experimental cell cycle life test curve that the electrode obtained using embodiment 4 is prepared as anode；Grid Lead-acid battery cycle life reaches 324 times after alloy surface deposition slicker solder/graphene composite coating.

Claims (10)

1. a kind of preparation method containing slicker solder/graphene composite coating lead-acid battery electrode, it is characterised in that: by following Step carries out:
One, the pretreatment of lead acid accumulator plate grid: lead acid accumulator plate grid successively washed, oil removing, etch processing；
Two, slicker solder/graphene composite coating deposition: the grid immersion that step 1 is handled well is contained into lead fluoborate, fluoboric acid is sub- In aqueous solution, that is, electric depositing solution of tin, fluoboric acid, boric acid, peptone and graphene, electro-deposition is made with slicker solder/graphite The grid of alkene composite coating；
Three, the preparation of lead-acid battery electrode: step 2 preparation is successively passed through with slicker solder/graphene composite coating grid Surface full-filling lead plaster and curing and drying processing, are prepared containing slicker solder/graphene composite coating lead-acid battery electrode.
2. preparation method according to claim 1, it is characterised in that: oil removing described in step 1 refers to the substrate after washing Material electrochemical deoiling 0.5~2.0 minute at 60~80 DEG C in alkaline degreasing liquid, then ultrasonic cleaning 5 in deionized water ~15 minutes.
3. preparation method according to claim 2, it is characterised in that: the alkaline degreasing liquid be containing sodium hydroxide 20~ The aqueous solution of 20~30g/L of 30g/L and sodium carbonate.
4. preparation method according to claim 1, it is characterised in that: etch described in step 1 refers to the substrate after oil removing Material impregnates 1 minute in etching solution, and the etching solution is hydrofluoric acid 50~500mL/L and 30wt.% containing 40wt.% 10~70mL/L of hydrogen peroxide aqueous solution.
5. preparation method according to claim 1, it is characterised in that: electric depositing solution each component concentration described in step 2 Are as follows: 100~1000g/L of lead fluoborate, 10~80g/L of stannous fluoboric acid, 50~400g/L of fluoboric acid, 1~15g/L of boric acid, egg White 0.1~1.5g/L of peptone, 0.01~1g/L of graphene.
6. preparation method according to claim 1, it is characterised in that: electro-deposition described in step 2, condition are as follows: 10~ 100mA constant current, 5~60min of electro-deposition.
7. preparation method according to claim 1, it is characterised in that: lead plaster described in step 3 containing lead powder, red lead, gathers Tacryl, distilled water and sulfuric acid.
8. preparation method according to claim 7, it is characterised in that: in the lead plaster, each component presses lead powder: red lead: poly- Tacryl: distilled water: sulfuric acid weight percent is 3000:800:6:(50-150): 800.
9. preparation method according to claim 1, it is characterised in that: full-filling lead plaster described in step 3, lead plaster temperature when full-filling Degree is 45 DEG C, full-filling thickness are as follows: 2mm is dipped in the 1.14g/cm that density is after the completion of the operation of full-filling lead plaster3Sulfuric acid it is molten In liquid, taken out after being kept for 3~5 seconds.
10. preparation method according to claim 1, it is characterised in that: dry solidification described in step 3, specifically: full-filling Grid after lead plaster solidifies 24 hours under conditions of 72 DEG C, relative humidity > 90%, and then drying 36 is small under the conditions of 62 DEG C When.
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CN111540906A (en) * 2020-04-22 2020-08-14 天能电池集团股份有限公司 Preparation method of surface coating for storage battery grid and storage battery positive grid for deep circulation
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