CN106531972A - Preparation method of lead-graphene composite material for lead-carbon battery - Google Patents
Preparation method of lead-graphene composite material for lead-carbon battery Download PDFInfo
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- CN106531972A CN106531972A CN201610718669.3A CN201610718669A CN106531972A CN 106531972 A CN106531972 A CN 106531972A CN 201610718669 A CN201610718669 A CN 201610718669A CN 106531972 A CN106531972 A CN 106531972A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005119 centrifugation Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract 2
- 230000000996 additive effect Effects 0.000 claims abstract 2
- 239000011259 mixed solution Substances 0.000 claims description 82
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 16
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 15
- 239000004021 humic acid Substances 0.000 claims description 15
- 229920005610 lignin Polymers 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000007711 solidification Methods 0.000 claims description 12
- 230000008023 solidification Effects 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 230000014759 maintenance of location Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011505 plaster Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 229910000004 White lead Inorganic materials 0.000 claims description 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 229940046892 lead acetate Drugs 0.000 description 16
- 239000002253 acid Substances 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M16/00—Structural combinations of different types of electrochemical generators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
- H01M4/14—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- 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
-
- 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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- Materials Engineering (AREA)
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Abstract
The invention provides a preparation method of a lead-graphene composite material for a lead-carbon battery. The lead-graphene composite material is prepared by adopting simple methods of liquid-phase reaction, centrifugation, high-temperature sintering and the like. The process is simple, the production efficiency is high, implementation of large-scale production is facilitated and popularization and application are facilitated. The obtained lead-graphene composite material has high hydrogen evolution overpotential, the problem of low hydrogen evolution overpotential of graphene is well solved and the capacitance performance of the graphene is improved. According to the composite material serving as an additive for a negative electrode of the lead-carbon battery, the rate capability and the charge acceptance of the battery can be effectively improved, the cycle life of an HRPSOC can be effectively prolonged, the water loss of the lead-carbon battery is reduced and the application prospect is wide.
Description
Technical field
The invention belongs to Graphene applied technical field, and in particular to a kind of lead carbon battery lead-Graphene composite wood
The preparation method of material.
Background technology
2004, Univ Manchester UK physicist successfully isolated Graphene from graphite, and Graphene has had
Beautiful two dimensional crystal structure, its lattice are the hexagons surrounded by six carbon atom, and thickness is an atomic layer.Carbon atom it
Between it is bonded by σ, combination is sp2Hydridization, these σ keys impart the extremely excellent mechanical property of Graphene and structure is firm
Property.In Graphene, each carbon atom has the p electronics of a non-bonding, and these p electronics can be moved freely in crystal,
Impart the good electric conductivity of Graphene.Due to characteristics such as Graphene high conductivity, high intensity, ultra-thins so that Graphene exists
The fields such as solar cell, sensor, nanoelectronics, high-performance nanometer electronic device, gas sensor and energy stores have
It is widely applied prospect so as to become study hotspot in recent years.
Lead carbon battery is a kind of new superbattery, is to unify both lead-acid battery and ultracapacitor：Both played
The advantage that super capacitor moment Large Copacity charges, has also played the specific energy advantage of lead-acid battery, and has possessed extraordinary filling
Discharge performance.Graphene is incorporated in lead carbon battery negative material, negative pole sulfation phenomenon is prevented, is improve battery
HRPSoC cycle lives and charge acceptance.But as the overpotential of hydrogen evolution of Graphene is relatively low, negative pole liberation of hydrogen can be aggravated and asked
Topic, makes battery dehydration serious, and maintenance-free performance is reduced.The presence of this problem limits lead carbon battery wider, more
The application of wide field.
The content of the invention
It is an object of the invention to solve the deficiencies in the prior art and shortcoming, there is provided one kind is by simple chemical synthesis
The method for preparing lead carbon battery lead-graphene composite material.The present invention is burnt using simple liquid phase reactor, centrifugation, high temperature
The methods such as knot prepare lead-graphene composite material, and process is simple, the lead-Graphene of gained have high overpotential of hydrogen evolution, very well
Solve the problems, such as that Graphene overpotential of hydrogen evolution is low.
The present invention technology path be：With Graphene and plumbi nitras or lead acetate as raw material, prepared by chemical reaction
Lead-graphene composite material, is then added to prepared lead-graphene composite material in the negative pole of lead carbon battery.
1) a kind of lead carbon battery lead-graphene composite material preparation method, it is characterised in that comprise the steps：
1.1) soluble lead salt is dissolved in deionized water according to certain mass volume ratio, obtains mixed solution A；
1.2) graphene uniform is distributed to into step 1.1 according to certain mass volume ratio) the middle mixed solution A for preparing
In, obtain mixed solution B；
1.3) certain density aqueous slkali is added into step 1.2 according to certain volume ratio) the middle mixed solution B for preparing,
Obtain mixed solution C；
1.4) by step 1.3) the middle mixed solution C centrifugation for preparing, sediment is collected, is then washed with cleaning solution repeatedly
Wash, until centrifugate reaches neutral (i.e. pH reaches 7), obtain solid residue；
1.5) by step 1.4) in prepare residue carry out the forerunner that freeze-drying obtains lead-graphene composite material
Body；
1.6) by step 1.5) in lead-graphene composite material presoma for preparing under an inert atmosphere, be heated to certain
Temperature, and held for some time, take out after being cooled to room temperature, obtain final lead-graphene composite material.
Step 1.1) described in soluble lead salt be plumbi nitras, lead acetate it is therein one or two, described is solvable
Property lead salt and deionized water mass volume ratio be 0.1～0.5g: 100ml；
Step 1.2) described in Graphene Average Particle Diameters be 5～35 μm, specific surface area be 500～1200m2/ g,
The number of plies is 2～10 layers, and described Graphene is 0.05～1.00g: 100ml with the mass volume ratio of mixed solution A；
Step 1.3) described in aqueous slkali be NaOH, KOH, Na2CO3、NaHCO3, one or more in ammoniacal liquor, it is described
The pH value of aqueous slkali is 8～14, the volume ratio 1～10ml: 100ml of the aqueous slkali and mixed solution B；
Step 1.4) described in centrifugal rotational speed be 2000～5000r/min, centrifugation time be 3～15min, used washes
Solution is washed for one or two in deionized water and ethanol；
Step 1.5) described in freeze-drying temperature be -50～-80 DEG C, vacuum be 1～20Pa, described lead-stone
In the presoma of black alkene composite, contained basic lead carbonate is regular hexagon, and mean particle size is 500～900nm；
Step 1.6) described in inert atmosphere be argon gas or nitrogen, be heated to 300～500 DEG C, temperature retention time is 1-
3h, the lead-graphene composite material prepared used as lead carbon electrode negative material, wherein lead-graphene composite material
Addition is 0.1%～1.0% of lead powder quality in negative pole.
2) preparation method of lead carbon battery negative pole, its feature comprise the steps：
2.1) according to lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid: deionization
The mass ratio of water be 90～100g: 8.5～10g: 0.5～1.0g: 0.1～0.15g: 0.1～1.0g: 0.1～0.3g: 0.1～
0.3g: 10～15g weighs above material, and the wherein density of sulfuric acid is 1.24～1.28g/cm3；
2.2) by step 2.1) described in lead-graphene composite material evenly spread to step 2.1) in deionized water
In, obtain in mixed solution D；
2.3) by step 2.1) in barium sulfate, lead-graphene composite material, chopped fiber, lignin, humic acid, lead powder do
Mixed 5～10min, obtains compound A；
2.4) by step 2.2) in prepare mixed solution D be added to step 2.3) in prepare compound A in, quickly stir
5～10min is mixed, compound B is obtained；
2.5) by step 2.1) in sulfuric acid be added in 5min in compound B, it is quick to stir, obtain cathode lead plaster；
2.6) by step 2.5) in lead plaster be quickly coated onto on negative electrode grid, the solidification temperature of pole plate is 40～60 DEG C,
Humidity is 60%～99%, and the time is 24～48h, and baking temperature is 40～60 DEG C, and the time is 12～24h, finally gives lead carbon
Cell negative plate.
The present invention is mainly had the following effects using after above-mentioned technical proposal：
1. the present invention prepares lead-graphene composite material using liquid phase reactor, centrifugation and simple chemical reaction, work
Skill is simple, easy to operate, and production efficiency is high, is advantageously implemented large-scale production, easy to utilize；
2. lead-graphene composite material that the present invention is prepared improves the relatively low shortcoming of Graphene overpotential of hydrogen evolution, drop
The water loss of low lead carbon battery.
3. lead-graphene composite material that the present invention is prepared, improves the capacitive property of Graphene, is added to lead carbon electricity
The capacity of battery is improve in pond.
4., after lead-graphene composite material that the present invention is prepared is added to lead carbon battery negative pole, lead carbon electricity is improve
The high rate performance in pond, charge acceptance and HRPSOC cycle lives.
Description of the drawings
Fig. 1 is the SEM figures of lead carbon battery lead-graphene composite material presoma that the present embodiment 1 is prepared.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
1) a kind of preparation method of lead carbon battery lead-graphene composite material, wherein：
1.1) take soluble lead salt to be added in deionized water, according to soluble lead salt: deionized water ratio is 0.1g:
100ml is configured, and obtains mixed solution A, and wherein soluble lead salt is plumbi nitras；
1.2) take Graphene to be added in mixed solution A, according to Graphene: mixed solution A ratio is matched somebody with somebody for 0.05g: 100ml
Put, obtain mixed solution B；
1.3) take aqueous slkali to be added in mixed solution B, according to aqueous slkali: mixed solution B ratios are matched somebody with somebody for 1ml: 100ml
Put, obtain mixed solution C, wherein aqueous slkali is NaOH solution, and pH value is 14；
1.4) by the mixed solution C centrifugation prepared in step 3, sediment is collected, is washed with cleaning solution, until centrifugation
Liquid reaches neutral (i.e. pH reaches 7), obtains solid residue, and wherein cleaning solution is deionized water, rotating speed 2000r/ during centrifugation
Min, centrifugation time are 15min；
1.5) solid residue prepared in step 4 is carried out into the forerunner that freeze-drying obtains lead-graphene composite material
Body, wherein cryodesiccated condition are -80 DEG C, 10Pa；
1.6) presoma of the lead-graphene composite material prepared in step 5 is heated under the protective atmosphere of nitrogen
300 DEG C, 3h is incubated, takes out after being cooled to room temperature, obtain lead-graphene composite material.
2) preparation method of lead carbon battery negative pole, wherein：
2.1) according to lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid: deionization
The mass ratio of water weighs above material, the wherein density of sulfuric acid for 90g: 8.5g: 0.5g: 0.05g: 0.1g: 0.1g: 0.1g: 10g
For 1.24g/cm3；
2.2) by step 2.1) described in lead-graphene composite material evenly spread to step 2.1) in deionized water
In, obtain in mixed solution D；
2.3) by step 2.1) in barium sulfate, lead-graphene composite material, chopped fiber, lignin, humic acid, lead powder do
Mixed 5min, obtains compound A；
2.4) by step 2.2) in prepare mixed solution D be added to step 2.3) in prepare compound A in, quickly stir
5min is mixed, compound B is obtained；
2.5) by step 2.1) in sulfuric acid be added in 5min in compound B, it is quick to stir, obtain cathode lead plaster；
2.6) by step 2.5) in lead plaster be quickly coated onto on negative electrode grid, the solidification temperature of pole plate is 40 DEG C, humidity
For 60%, the time is 24h, and baking temperature is 40 DEG C, and the time is 12h, finally gives lead carbon battery negative plate.
Embodiment 2
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Step 1.1) described in soluble lead salt be plumbi nitras, the mixed solution A is according to plumbi nitras: deionized water
Ratio is 0.25g: 100ml configuration；
Step 1.2) described in mixed solution B according to Graphene: mixed solution A ratio be 0.5g: 100ml configuration；
Step 1.3) described in mixed solution C according to aqueous slkali: mixed solution B ratios be 5ml: 100ml configuration, wherein
Aqueous slkali is KOH solution, and pH value is 10；
Step 1.4) described in cleaning solution be absolute ethyl alcohol, during centrifugation, centrifugal rotational speed is 5000r/min, and centrifugation time is
3min；
Step 1.5) described in freeze-drying temperature be -70 DEG C, vacuum is 10Pa；
Step 1.6) described in protective atmosphere be argon gas, heating-up temperature be 500 DEG C, temperature retention time is 1h.
2) preparation of lead carbon battery negative pole, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 100g: 10g: 1.0g: 0.15g: 1.0g: 0.3g: 0.3g: 15g
Density 1.28g/cm of acid3；
Step 2.3) described in the dry-mixed time be 10min；
Step 2.4) described in quick mixing time be 10min；
Step 2.6) described in the solidification temperature of pole plate be 60 DEG C, humidity is 99%, and the time is 48h, and baking temperature is
60 DEG C, the time is 24h.
Embodiment 3
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Soluble lead salt described in step (1) is plumbi nitras, and the mixed solution A is according to plumbi nitras: deionized water
Ratio is 0.25g: 100ml configuration；
Mixed solution B described in step (2) is according to Graphene: mixed solution A ratio is 0.5g: 100ml configuration；
Mixed solution C described in step (3) is according to aqueous slkali: mixed solution B ratios are 10ml: 100ml configuration, wherein
Aqueous slkali is Na2CO3Solution, pH value are 8；
Cleaning solution described in step (4) is absolute ethyl alcohol, and during centrifugation, centrifugal rotational speed is 4000r/min, and centrifugation time is
8min；
Freeze-drying temperature described in step (5) is -50 DEG C, and vacuum is 20Pa；
Protective atmosphere described in step (6) is nitrogen, and heating-up temperature is 500 DEG C, and temperature retention time is 1h.
2) preparation of lead carbon battery negative pole, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 95g: 9g: 0.75g: 0.1g: 0.6g: 0.2g: 0.2g: 12.5g
Density 1.26g/cm of acid3；
Step 2.3) described in the dry-mixed time be 7min；
Step 2.4) described in quick mixing time be 7min；
Step 2.6) described in the solidification temperature of pole plate be 50 DEG C, humidity is 85%, and the time is 36h, and baking temperature is
50 DEG C, the time is 18h.
Embodiment 4
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Soluble lead salt described in step (1) is lead acetate, and the mixed solution A is according to lead acetate: deionized water
Ratio is 0.1g: 100ml configuration；
Mixed solution B described in step (2) is according to Graphene: mixed solution A ratio is 0.05g: 100ml configuration；
Mixed solution C described in step (3) is according to aqueous slkali: mixed solution B ratios are 5ml: 100ml configuration, wherein
Aqueous slkali is ammoniacal liquor, and pH value is 10；
Cleaning solution described in step (4) is deionized water, and during centrifugation, centrifugal rotational speed is 2000r/min, and centrifugation time is
15min；
Freeze-drying temperature described in step (5) is -50 DEG C, and vacuum is 20Pa；
Protective atmosphere described in step (6) is nitrogen, and heating-up temperature is 500 DEG C, and temperature retention time is 1h.
2) preparation of lead carbon battery negative pole, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 90g: 8.5g: 0.5g: 0.05g: 0.1g: 0.1g: 0.1g: 10g
Density 1.28g/cm of acid3；
Step 2.3) described in the dry-mixed time be 10min；
Step 2.4) described in quick mixing time be 10min；
Step 2.6) described in the solidification temperature of pole plate be 60 DEG C, humidity is 99%, and the time is 48h, and baking temperature is
60 DEG C, the time is 24h.
Embodiment 5
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Soluble lead salt described in step (1) is lead acetate, and the mixed solution A is according to lead acetate: deionized water
Ratio is 0.5g: 100ml configuration；
Mixed solution B described in step (2) is according to Graphene: mixed solution A ratio is 1.0g: 100ml configuration；
Mixed solution C described in step (3) is according to aqueous slkali: mixed solution B ratios are 7ml: 100ml configuration, wherein
Aqueous slkali is NaHCO3Solution, pH value are 12；
Cleaning solution described in step (4) is absolute ethyl alcohol, and during centrifugation, centrifugal rotational speed is 3000r/min, and centrifugation time is
5min；
Freeze-drying temperature described in step (5) is -80 DEG C, and vacuum is 20Pa；
Protective atmosphere described in step (6) is argon gas, and heating-up temperature is 300 DEG C, and temperature retention time is 3h.
2) preparation of lead carbon battery negative plate, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 100g: 10g: 1.0g: 0.15g: 1.0g: 0.3g: 0.3g: 15g
Density 1.28g/cm of acid3；
Step 2.3) described in the dry-mixed time be 10min；
Step 2.4) described in quick mixing time be 10min；
Step 2.6) described in the solidification temperature of pole plate be 60 DEG C, humidity is 99%, and the time is 48h, and baking temperature is
60 DEG C, the time is 24h.
Embodiment 6
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Soluble lead salt described in step (1) is lead acetate, and the mixed solution A is according to lead acetate: deionized water
Ratio is 0.25g: 100ml configuration；
Mixed solution B described in step (2) is according to Graphene: mixed solution A ratio is 0.5g: 100ml configuration；
Mixed solution C described in step (3) is according to aqueous slkali: mixed solution B ratios are 5ml: 100ml configuration, wherein
Aqueous slkali is NaOH solution, and pH value is 8；
Cleaning solution described in step (4) is absolute ethyl alcohol, and during centrifugation, centrifugal rotational speed is 4000r/min, and centrifugation time is
10min；
Freeze-drying temperature described in step (5) is -50 DEG C, and vacuum is 10Pa；
Protective atmosphere described in step (6) is argon gas, and heating-up temperature is 400 DEG C, and temperature retention time is 1.5h.
2) preparation of lead carbon battery negative pole, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 95g: 9g: 0.75g: 0.1g: 0.6g: 0.2g: 0.2g: 12.5g
Density 1.26g/cm of acid3；
Step 2.3) described in the dry-mixed time be 7min；
Step 2.4) described in quick mixing time be 7min；
Step 2.6) described in the solidification temperature of pole plate be 50 DEG C, humidity is 85%, and the time is 36h, and baking temperature is
50 DEG C, the time is 18h.
Embodiment 7
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Soluble lead salt described in step (1) is the mixture of plumbi nitras and lead acetate, and the mixed solution A is according to nitre
Lead plumbate: lead acetate: the ratio of deionized water is 0.25g: 0.25g: 100ml configuration；
Mixed solution B described in step (2) is according to Graphene: mixed solution A ratio is 0.5g: 100ml configuration；
Mixed solution C described in step (3) is according to aqueous slkali: mixed solution B ratios are 1ml: 100ml configuration, wherein
Mixed solution of the aqueous slkali for KOH and NaOH, pH value is 14；
Cleaning solution described in step (4) is the mixed solution of absolute ethyl alcohol and deionized water, according to absolute ethyl alcohol: go from
The proportional arrangement of sub- water 50ml: 50ml, during centrifugation, centrifugal rotational speed is 2000r/min, and centrifugation time is 15min；
Freeze-drying temperature described in step (5) is -80 DEG C, and vacuum is 10Pa；
Protective atmosphere described in step (6) is nitrogen, and heating-up temperature is 300 DEG C, and temperature retention time is 3h.
2) preparation of lead carbon battery negative pole, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 90g: 8.5g: 0.5g: 0.05g: 0.3g: 0.1g: 0.1g: 10g
Density 1.26g/cm of acid3；
Step 2.3) described in the dry-mixed time be 5min；
Step 2.4) described in quick mixing time be 5min；
Step 2.6) described in the solidification temperature of pole plate be 40 DEG C, humidity is 75%, and the time is 36h, and baking temperature is
50 DEG C, the time is 24h.
Embodiment 8
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Soluble lead salt described in step (1) is the mixture of plumbi nitras and lead acetate, and the mixed solution A is according to nitre
Lead plumbate: lead acetate: the ratio of deionized water is 0.1g: 0.2g: 100ml configuration；
Mixed solution B described in step (2) is according to Graphene: mixed solution A ratio is 0.5g: 100ml configuration, ultrasound
Dispersion 1；
Mixed solution C described in step (3) is according to aqueous slkali: mixed solution B ratios are 5ml: 100ml configuration, wherein
Aqueous slkali is the mixed solution of KOH and ammoniacal liquor, and pH value is 10；
Cleaning solution described in step (4) is the mixed solution of absolute ethyl alcohol and deionized water, according to absolute ethyl alcohol: go from
The proportional arrangement of sub- water 70ml: 30ml, during centrifugation, centrifugal rotational speed is 4000r/min, and centrifugation time is 10min；
Freeze-drying temperature described in step (5) is -65 DEG C, and vacuum is 15Pa；
Protective atmosphere described in step (6) is argon gas gas, and heating-up temperature is 400 DEG C, and temperature retention time is 2h.
2) preparation of lead carbon battery negative pole, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 100g: 10g: 1.0g: 0.15g: 1.5g: 0.3g: 0.3g: 15g
Density 1.28g/cm of acid3；
Step 2.3) described in the dry-mixed time be 7min；
Step 2.4) described in quick mixing time be 7min；
Step 2.6) described in the solidification temperature of pole plate be 60 DEG C, humidity is 99%, and the time is 48h, and baking temperature is
60 DEG C, the time is 24h.
Embodiment 9
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Soluble lead salt described in step (1) is the mixture of plumbi nitras and lead acetate, and the mixed solution A is according to nitre
Lead plumbate: lead acetate: the ratio of deionized water is 0.2g: 0.3g: 100ml configuration；
Mixed solution B described in step (2) is according to Graphene: mixed solution A ratio is 0.5g: 100ml configuration；
Mixed solution C described in step (3) is according to aqueous slkali: mixed solution B ratios are 10ml: 100ml configuration, wherein
Aqueous slkali is KOH and NaHCO3Mixed solution, pH value is 8；
Cleaning solution described in step (4) is the mixed solution of absolute ethyl alcohol and deionized water, according to absolute ethyl alcohol: go from
The proportional arrangement of sub- water 30ml: 70ml, during centrifugation, centrifugal rotational speed is 2000r/min, and centrifugation time is 15min；
Freeze-drying temperature described in step (5) is -80 DEG C, and vacuum is 10Pa；
Protective atmosphere described in step (6) is nitrogen, and heating-up temperature is 500 DEG C, and temperature retention time is 1h.
2) preparation of lead carbon battery negative pole, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 90g: 8.5g: 0.5g: 0.05g: 0.2g: 0.1g: 0.1g: 10g
Density 1.24g/cm of acid3；
Step 2.3) described in the dry-mixed time be 7min；
Step 2.4) described in quick mixing time be 7min；
Step 2.6) described in the solidification temperature of pole plate be 60 DEG C, humidity is 85%, and the time is 48h, and baking temperature is
60 DEG C, the time is 24h.
Embodiment 10
1) a kind of preparation method of lead carbon battery lead-graphene composite material, with case study on implementation 1, wherein：
Soluble lead salt described in step (1) is the mixture of plumbi nitras and lead acetate, and the mixed solution A is according to nitre
Lead plumbate: lead acetate: the ratio of deionized water is 0.4g: 0.1g: 100ml configuration；
Mixed solution B described in step (2) is according to Graphene: mixed solution A ratio is 0.5g: 100ml configuration；
Mixed solution C described in step (3) is according to aqueous slkali: mixed solution B ratios are 3ml: 100ml configuration, wherein
Aqueous slkali is KOH and Na2CO3Mixed solution, pH value is 14；
Cleaning solution described in step (4) is the mixed solution of absolute ethyl alcohol and deionized water, according to absolute ethyl alcohol: go from
The proportional arrangement of sub- water 30ml: 70ml, during centrifugation, centrifugal rotational speed is 2000r/min, and centrifugation time is 15min；
Freeze-drying temperature described in step (5) is -80 DEG C, and vacuum is 10Pa；
Protective atmosphere described in step (6) is nitrogen, and heating-up temperature is 500 DEG C, and temperature retention time is 1h.
2) preparation of lead carbon battery negative pole, with case study on implementation 1, wherein：
Step 2.1) described in lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid
: the mass ratio of deionized water weighs above material, wherein sulphur for 95g: 9g: 0.75g: 0.1g: 1.0g: 0.2g: 0.2g: 12.5g
Density 1.26g/cm of acid3；
Step 2.3) described in the dry-mixed time be 7min；
Step 2.4) described in quick mixing time be 7min；
Step 2.6) described in the solidification temperature of pole plate be 40 DEG C, humidity is 60%, and the time is 48h, and baking temperature is
50 DEG C, the time is 24h.
Claims (8)
1. a kind of preparation method of lead carbon battery lead-graphene composite material, it is characterised in that comprise the steps：
(1) soluble lead salt is dissolved in deionized water according to certain mass volume ratio, obtains mixed solution A；
(2) graphene uniform is distributed in the mixed solution A prepare in step (1) according to certain mass volume ratio, is obtained
Mixed solution B；
(3) certain density aqueous slkali is added according to certain volume ratio the mixed solution B prepared in step (2), is mixed
Close solution C；
(4) the mixed solution C centrifugation that will be prepared in step (3), collects sediment, then uses cleaning solution cyclic washing, directly
Neutral (i.e. pH reaches 7) is reached to centrifugate, obtain solid residue；
(5) solid residue prepared in step (4) is carried out into the presoma that freeze-drying obtains lead-graphene composite material；
(6) by the lead-graphene composite material presoma prepared in step (5) under an inert atmosphere, uniform temperature is heated to, and
Held for some time, takes out after being cooled to room temperature, obtains final lead-graphene composite material.
2. method as described in claim 1, it is characterised in that the soluble lead salt described in step (1) is plumbi nitras or vinegar
Lead plumbate one or two, described soluble lead salt is 0.1～0.5g: 100ml with the mass volume ratio of deionized water.
3. method as described in claim 1, it is characterised in that the Graphene Average Particle Diameters described in step (2) are 5
～35 μm, specific surface area is 500～1200m2/ g, the number of plies are 2～10 layers, the mass body of described Graphene and mixed solution A
Product is than being 0.05～1.00g: 100ml.
4. method as described in claim 1, it is characterised in that the aqueous slkali described in step (3) be NaOH, KOH,
Na2CO3、NaHCO3, one or more in ammoniacal liquor, the pH value of the aqueous slkali is 8～14, the aqueous slkali and mixed solution B
Volume ratio 1～10ml: 100ml.
5. method as described in claim 1, it is characterised in that the centrifugation time described in step (4) is 3～15min, from
Heart rotating speed is 2000～5000r/min, and cleaning solution used is deionized water or the one kind in ethanol.
6. method as described in claim 1, it is characterised in that the freeze-drying temperature described in step (5) is -50～-80
DEG C, vacuum be 1～20Pa, in the presoma of described lead-graphene composite material, contained basic lead carbonate is positive six side
Shape, mean particle size are 500～900nm.
7. method as described in claim 1, it is characterised in that the inert atmosphere described in step (6) is argon gas or nitrogen
Gas, is heated to 300～500 DEG C, and temperature retention time is 1-3h, and the lead-graphene composite material prepared is used as the negative of lead carbon battery
Pole additive.
8. as recited in claim 7, it is characterised in that the preparation method of described lead carbon battery negative pole comprises the steps：
(1) according to lead powder: sulfuric acid: barium sulfate: chopped fiber: lead-graphene composite material: lignin: humic acid: the matter of deionized water
Amount is than being 90～100g: 8.5～10g: 0.5～1.0g: 0.05～0.15g: 0.1～1.0g: 0.1～0.3g: 0.1～0.3g:
10～15g weighs above material, and the wherein density of sulfuric acid is 1.24～1.28g/cm3；
(2) lead-graphene composite material in step (1) is evenly spread to into deionized water according to the quality proportioning of step (1)
In, obtain in mixed solution D；
(3) by the barium sulfate in step (1), lead-graphene composite material, chopped fiber, lignin, humic acid, lead powder dry-mixed 5～
10min, obtains compound A；
(4) the mixed solution D in step (3) is added in compound A, quickly stirs 5～10min, obtain compound B；
(5) sulfuric acid in step (1) is added in compound B in 5min, it is quick to stir, obtain cathode lead plaster；
(6) lead plaster in step (5) is quickly coated onto on negative electrode grid, the solidification temperature of pole plate is 40～60 DEG C, and humidity is
60%～99%, the time is 24～48h, and baking temperature is 40～60 DEG C, and the time is 12～24h, finally gives lead carbon battery
Negative pole.
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