CN109037598A - A kind of preparation method of slicker solder/graphene composite coating - Google Patents
A kind of preparation method of slicker solder/graphene composite coating Download PDFInfo
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- CN109037598A CN109037598A CN201810857504.3A CN201810857504A CN109037598A CN 109037598 A CN109037598 A CN 109037598A CN 201810857504 A CN201810857504 A CN 201810857504A CN 109037598 A CN109037598 A CN 109037598A
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/36—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
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of slicker solder/graphene composite coating preparation methods, belong to metal Surface Treatment Technique field, technical solution are as follows: 1) base material pre-processes: base material successively polished, washed, oil removing, etch processing；2) slicker solder/graphene composite coating deposition: the base material that step 1) is handled well being immersed and contains lead, tin, and in aqueous solution, that is, electric depositing solution of graphene, electro-deposition forms slicker solder/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, and environment friendly is strong, is consequently adapted to mass production；The slicker solder of preparation/graphene composite coating is applied to lead-acid accumulator, is remarkably improved its cyclical stability, prepared lead-acid accumulator cycle life under the conditions of 100% depth of discharge can reach 367 times.
Description
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 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.
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 (8)
1. a kind of slicker solder/graphene composite coating preparation method, it is characterised in that: the following steps are included:
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, fluoboric acid
In aqueous solution, that is, electric depositing solution of stannous, fluoboric acid, boric acid, peptone and graphene, it is multiple that electro-deposition forms slicker solder/graphene
Close coating.
2. preparation method according to claim 1, it is characterised in that: the step 1) base material is lead-acid accumulator plate
Alloy material for lattice.
3. preparation method according to claim 1, it is characterised in that: the step 1) polishing, specially by base material
With the resistance to silicon carbide paper polishing of 600#, 1000# and 2000#.
4. preparation method according to claim 1, it is characterised in that: the step 1) oil removing refers to the substrate material after washing
Material impregnates oil removing 0.5~2.0 minute in alkaline degreasing liquid at 60~80 DEG C, then in deionized water ultrasonic cleaning 5~
15 minutes.
5. preparation method according to claim 4, 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.
6. preparation method according to claim 1, it is characterised in that: the step 1) etch refers to the substrate material after oil removing
Material impregnates 1 minute in etching solution, and the etching solution is hydrofluoric acid 50~500mL/L and 30wt.% containing 40wt.%
The aqueous solution of 10~70mL/L of hydrogen peroxide.
7. preparation method according to claim 1, it is characterised in that: step 2) the electric depositing solution each component concentration 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, peptone
0.1~1.5g/L, 0.01~1g/L of graphene.
8. preparation method according to claim 1, it is characterised in that: the step 2) electro-deposition, condition are as follows: 10~100mA
Constant current, 5~60min of electro-deposition.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014063714A (en) * | 2012-03-02 | 2014-04-10 | Shinshu Univ | Negative electrode material for lithium ion battery and method of manufacturing the same |
| CN105132993A (en) * | 2015-08-28 | 2015-12-09 | 天能电池集团有限公司 | Lead tin-graphene composite material, as well as preparation method and application thereof |
| CN105206844A (en) * | 2015-08-28 | 2015-12-30 | 天能电池集团有限公司 | Preparation method of lead storage battery grid containing lead-graphene composite |
| CN105297011A (en) * | 2015-11-05 | 2016-02-03 | 华南理工大学 | Method for preparing super-hydrophobic composite film layer on surface of magnesium alloy |
| CN107230777A (en) * | 2017-07-26 | 2017-10-03 | 合肥尚强电气科技有限公司 | Lead paste for lead-acid storage battery and preparation method thereof |
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2018
- 2018-07-31 CN CN201810857504.3A patent/CN109037598B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014063714A (en) * | 2012-03-02 | 2014-04-10 | Shinshu Univ | Negative electrode material for lithium ion battery and method of manufacturing the same |
| CN105132993A (en) * | 2015-08-28 | 2015-12-09 | 天能电池集团有限公司 | Lead tin-graphene composite material, as well as preparation method and application thereof |
| CN105206844A (en) * | 2015-08-28 | 2015-12-30 | 天能电池集团有限公司 | Preparation method of lead storage battery grid containing lead-graphene composite |
| CN105297011A (en) * | 2015-11-05 | 2016-02-03 | 华南理工大学 | Method for preparing super-hydrophobic composite film layer on surface of magnesium alloy |
| CN107230777A (en) * | 2017-07-26 | 2017-10-03 | 合肥尚强电气科技有限公司 | Lead paste for lead-acid storage battery and preparation method thereof |
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