CN110212172A - A kind of composite material and preparation method of carbon material in-situ deposition nanometer lead crystal grain/lead oxide - Google Patents
A kind of composite material and preparation method of carbon material in-situ deposition nanometer lead crystal grain/lead oxide Download PDFInfo
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- CN110212172A CN110212172A CN201910387267.3A CN201910387267A CN110212172A CN 110212172 A CN110212172 A CN 110212172A CN 201910387267 A CN201910387267 A CN 201910387267A CN 110212172 A CN110212172 A CN 110212172A
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- lead
- carbon material
- carbon
- crystal grain
- mixed solution
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 100
- 239000005355 lead glass Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 36
- 230000008021 deposition Effects 0.000 title claims abstract description 35
- 229910000464 lead oxide Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims abstract 5
- 239000011259 mixed solution Substances 0.000 claims description 59
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 239000002134 carbon nanofiber Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 238000003828 vacuum filtration Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 239000011149 active material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 238000000859 sublimation Methods 0.000 description 7
- 230000008022 sublimation Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical class [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002258 gallium Chemical class 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 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
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 through mixing Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of composite material and preparation method of carbon material in-situ deposition nanometer lead crystal grain/lead oxide, the present invention obtain final products using carbon material and soluble lead salt as raw material, through techniques such as mixing, chemical precipitation, separation of solid and liquid, washing drying and high temperature sinterings.Present invention process is simple, easy to operate, and production cost is low, is advantageously implemented large-scale production, easy to promote and utilize；Have the characteristics that high conductivity, high overpotential of hydrogen evolution, high capacitance and excellent chemical property using product made from the method for the present invention.The method of the present invention can be widely used for the electrochmical power sources such as lead carbon battery, lithium ion battery, supercapacitor.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to arrive a kind of carbon material in-situ deposition nanometer lead crystal grain/oxygen
Change the composite material and preparation method of lead.
Background technique
Lead-acid battery passes through development in more than 150 years, because having raw material to be easy to get, it is cheap, have a safety feature, rate of recovery height
The advantages that, and the electric energy supply and storage of many economic fields such as be widely used in electric power, communication, military affairs, traffic, navigation and aviation
It can device.However the active material specific surface area of traditional lead acid batteries negative plate is small, quick charge is difficult, under HRPSoC operating condition
Easy sulfation makes pole plate fail, and battery cycle life is caused to greatly reduce so that the development of lead-acid battery lag behind it is other high
Performance novel battery.Lead carbon battery is using high-ratio surface, high-specific-power, the highly conductive, carbon material that has extended cycle life as cathode
A kind of novel lead-acid battery of additive.Carbon material is introduced into lead-acid battery cathode material by lead carbon battery, can effectively be hindered
Only cathode sulfation phenomenon improves the HPRSOC cycle life and charge acceptance of battery.But due to the analysis of carbon material
Hydrogen overpotential is lower, and in the charging later period of battery, violent evolving hydrogen reaction can occur for cathode, causes battery dehydration serious, causes
Battery failure.
In prior art, the patent of Publication No. CN104505262A discloses a kind of to be existed using the method for electro-deposition
Deposit lead on graphene is made lead graphene composite material, and the material is added in lead powder, and negative plate is made.Although by stone
The modified Combination that the two can be improved of black alkene, but effective contact area of lead active material and graphene is less, the two
In conjunction with not close, charge-discharge performance, power density and the cycle life of battery is caused not significantly improve, by graphene
Evolving hydrogen reaction and the water loss of initiation are not effectively suppressed.And production technology early period of the technology is complicated, it is difficult to real
It now industrializes, for electro-deposition waste liquid to environment there are larger pollution, environmentally friendly cost is big.Another prior art patent publication No. is
CN102306784A is disclosed and is loaded In on the activated carbon by ball-milling method or solvent precipitation2O3、Bi2O3、Ga2O3In one
Kind or several mixtures as liberation of hydrogen inhibitor improve the overpotential of hydrogen evolution of modified activated carbon.But pass through simple machine
The particle size for the loaded article that liberation of hydrogen inhibitor cannot uniformly be loaded on the carbon material, and obtained by tool mixing method is larger, easily
Reunite, cannot effectively play the effect of liberation of hydrogen inhibitor, such additive instead can generate the self discharge of battery
In addition negative influence also increases production cost to the cycling and reutilization of lead cathode.
Existing lead carbon battery C-base composte material and preparation method thereof, such as on September 28th, 2018 Publication No. announced
" a kind of the core-shell structure activated carbon negative electrode material and preparation method of lead carbon battery " patent of CN108598429A, it is disclosed compound
Material is spherical core-shell structure, and the shell of the spherical shape core-shell structure is active carbon, and core is the solid solution that bismuth salt-gallium salt is formed.It is public
The preparation method opened is that first organic carbon source is dissolved in deionized water to be formed in mixed solution addition reaction kettle, adds bismuth salt-
The solid solution that gallium salt is formed after high-temperature high-voltage reaction, is filtered, washed and is dried in vacuo, and is placed in protective gas atmosphere permanent
Temperature carbonizes, and obtains product after natural cooling.The major defect of the patent has: (1) resulting core-shell structure absorbent charcoal composite material
In, containing non-lead (bismuth, gallium) element, the self discharge reaction of lead carbon battery certainly will be increased, improve the recycling cost of lead cathode；
(2) cost of material is expensive, and bismuth salt and gallium salt used is necessary for bismuth nitrate, gallium nitrate；(3) in preparation method, bismuth salt-gallium salt shape
At solid solution needs carry out microwave sintering in the atmosphere of vapor and carbon dioxide, preparation condition is harsh, and process route is multiple
It is miscellaneous, and low output, it is unfavorable for large-scale industrial production.
Summary of the invention
Present invention aim to address the deficiencies in the prior art and disadvantage, and it is brilliant to provide a kind of carbon material in-situ deposition nanometer lead
The features such as composite material and preparation method of grain/lead oxide has simple process, easy to operate, and production cost is low, this is compound
Material has the characteristics that high hydrogen-evolution overpotential, highly conductive, high capacitance, and gained composite material is added in lead cathode, can make lead carbon
Battery HRPSoC cycle life extends at least 5 times, and charge efficiency improves 1.6 times, and water loss is only 0.1g/Ah, well below
The 1g/Ah (GB/T 5008.1-2013) of national standard.
Realizing the technical solution of the object of the invention is: a kind of carbon material in-situ deposition nanometer lead crystal grain/lead oxide composite wood
Material is carbon material surface in-situ deposition nanometer lead crystal grain/lead oxide composite material.The component and its quality percentage of the material
Number are as follows:
Carbon material 10~90%
Nanometer lead crystal grain 80~5%
Lead oxide 10~5%
Wherein: the carbon material is carbon nanotube or active carbon or carbon nano-fiber or graphene nanometer sheet or oxidation stone
Ink, phosphorus content is at least 90% or more；The partial size of nanometer lead crystal grain is 30~500nm；The partial size of lead oxide is 10~300nm.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, with carbon material and solvable
Property lead salt and aqueous slkali be raw material, through mixing, liquid phase reactor, separation of solid and liquid, washing be dry and the simple process of sintering obtains
Product.The method comprises the following specific steps that:
(1) according to the quality (g) of soluble lead salt: the ratio between volume (ml) of deionized water is the ratio of 0.1~0.6:500
Example, soluble lead salt is dissolved into deionized water, obtains mixed solution A after being sufficiently stirred；
(2) according to the quality (g) of carbon material: the ratio between volume (ml) of mixed solution A is the ratio of 1:500, by carbon material
It evenly spreads in mixed solution A, is mixed 10~30 minutes at room temperature, obtain the mixing of carbon material and soluble lead salt
Solution B；
Wherein: the carbon material is carbon nanotube or active carbon or carbon nano-fiber or graphene nanometer sheet or oxidation stone
Ink；
(3) according to aqueous slkali: the volume ratio of mixed solution B is the ratio of 1:50, and certain density aqueous slkali is slowly added
Enter to mixed solution B, is mixed 10~30 minutes at room temperature, obtains mixed solution C；
Wherein: the aqueous slkali is KOH or NaOH or Na2CO3Or NaHCO3Or ammonium hydroxide, concentration 1mol/L；
(4) (3) resulting mixed solution C is separated by solid-liquid separation, is washed with one or both of deionized water and ethyl alcohol
Solution is washed to wash repeatedly, until filtrate reaches neutral (i.e. pH reaches 7), by the solids finally collected be placed in -50~-80 DEG C,
Vacuum degree is to be freeze-dried 4~24 hours under 1~10Pa, obtains carbon material in-situ deposition nanometer lead crystal grain/lead oxide composite wood
The presoma of material；
Wherein: the separation of solid and liquid is centrifuge separation or vacuum filtration, and the revolving speed of centrifuge separation is 2000~4000r/
Min, the vacuum degree of vacuum filtration are -0.09~-0.1MPa；
(5) (4) resulting presoma is heated in inert gas 300~600 DEG C, and keeps the temperature 2~6 hours, it is cooling
Carbon material in-situ deposition nanometer lead crystal grain/lead oxide composite material can be prepared after to room temperature.
Wherein: the inert gas is high-purity nitrogen or argon gas or helium；
The present invention is after adopting the above technical scheme, mainly have the following effects:
(1) present invention uses cheap, and has the carbon material of high conduction performance and physical and chemical stability energy as load
Body improves carbon material and lead by nanometer lead crystal grain/lead oxide growth in situ on the surface of carbon material at all from structure
Combination farthest improves so that the carbon material as carrier is combined into an entirety with the active material as lead
The being tightly combined property of lead crystal grain and carbon material, it is evenly dispersed in carbon material carrier fundamentally to solve lead active material
Property problem, has contained the agglomeration of lead crystal grain and lead oxide, has provided advantageous item for the redox reaction of lead active material
Part has effectively played the utilization rate of lead active material, significantly suppresses the sulfation of lead cathode；
(2) nanometer lead crystal grain and lead oxide are evenly dispersed in the surface of carbon material by method provided by the invention, significantly
The hydrogen-evolution overpotential, capacitor and specific gravity of carbon material are improved, chemical property is superior.Resulting composite wood item is added to lead carbon
In the cathode of battery, the high rate performance, charge acceptance and HRPSOC cycle life of lead carbon battery are significantly improved, is reduced
The water loss of battery；
(3) the used liquid phase reactor of the method for the present invention, centrifugation and simple chemical reaction prepare carbon material supported lead/oxygen
Change lead composite material, simple process is easy to operate, and high production efficiency, environmental pressure is small, is conducive to large-scale production.
The method of the present invention can be widely used for preparation nanometer lead crystal grain composite material, using product made from the method for the present invention,
It can be widely applied to the electrochmical power sources such as lead carbon battery, lithium ion battery, supercapacitor.
Detailed description of the invention
Fig. 1 is carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material SEM electricity that the present embodiment 1 is prepared
Mirror figure.
Specific embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
A kind of component and its mass percent of carbon material in-situ deposition nanometer lead/lead oxide crystal grain composite material are as follows:
Carbon material 80%
Nanometer lead crystal grain 15%
Lead oxide 5%
Wherein: the carbon material is graphene nanometer sheet.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, the specific steps of which are as follows:
(1) according to the quality (g) of plumbi nitras: the ratio between volume (ml) of deionized water is the ratio of 0.1:500, by plumbi nitras
It is dissolved into deionized water, obtains mixed solution A after being sufficiently stirred.
(2) according to the quality (g) of carbon material: the ratio between volume of mixed solution A (ml) is the ratio of 1:500, by carbon material
It evenly spreads in mixed solution A, is mixed 10 minutes at room temperature, obtain the mixed solution of carbon material and soluble lead salt
B。
Wherein: the carbon material is graphene nanometer sheet.
(3) according to aqueous slkali: the volume ratio of mixed solution B is the ratio of 1:50, and certain density aqueous slkali is slowly added
Enter to mixed solution B, is mixed 10 minutes at room temperature, obtains mixed solution C.
Wherein: the aqueous slkali is NaOH.
(4) mixed solution C prepared in (3) step is separated by solid-liquid separation, with one of deionized water and ethyl alcohol or
Two kinds of washing solution wash repeatedly, until filtrate reaches neutral (i.e. pH reaches 7), by the solids finally collected be placed in -50 DEG C,
Vacuum degree is to be freeze-dried 12h under 10Pa, obtains carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material forerunner
Body.
Wherein: the separation of solid and liquid is centrifuge separation, and the revolving speed of centrifuge separation is 3000r/min.
(5) (4) resulting presoma is heated in inert gas 300 DEG C, and keeps the temperature 6h, after being cooled to room temperature
Carbon material in-situ deposition nanometer lead crystal grain/lead oxide composite material is prepared.
Embodiment 2
A kind of component and its mass percent of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material are as follows:
Carbon material 70%
Nanometer lead crystal grain 24%
Lead oxide 6%
Wherein: the carbon material is carbon nanotube.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, with embodiment 1, in which:
In (1) step, mixed solution A according to plumbi nitras quality (g): the ratio between volume (mL) of deionized water be 0.2:
500 proportional arrangement.
In (2) step, mixed solution B according to carbon material quality (g): the ratio between volume (mL) of mixed solution A be 1:500
Proportional arrangement, stir 15 minutes.Wherein: the carbon material is carbon nanotube.
In (3) step, mixed solution C is according to aqueous slkali: the volume ratio of mixed solution B is the proportional arrangement of 1:50, stirring
15 minutes.Wherein: the aqueous slkali is KOH solution.
In (4) step, freeze-drying temperature is -60 DEG C, vacuum degree 8Pa, sublimation drying 20.Wherein: described
Separation of solid and liquid be vacuum filtration, vacuum degree be -0.095MPa.
In (5) step, heating temperature is 400 DEG C, soaking time 5h.
Embodiment 3
A kind of component and its mass percent of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material are as follows:
Carbon material 60%
Nanometer lead crystal grain 33%
Lead oxide 7%
Wherein: the carbon material is active carbon.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, with embodiment 1, in which:
In (1) step, mixed solution A according to plumbi nitras quality (g): the volume (mL) of deionized water is 0.3:500
Proportional arrangement.
In (2) step, mixed solution B according to carbon material quality (g): the volume (mL) of mixed solution A be 1:500 ratio
Example configuration, is stirred 18 minutes.Wherein: the carbon material is active carbon.
In (3) step, mixed solution C is according to aqueous slkali: the volume ratio of mixed solution B is the proportional arrangement of 1:50, stirring
18 minutes.Wherein: the aqueous slkali is NaCO3Solution.
In (4) step, freeze-drying temperature is -70 DEG C, vacuum degree 6Pa, sublimation drying 20h.Wherein: described
Separation of solid and liquid be centrifuge separation, revolving speed 3800r/min.
In (5) step, heating temperature is 450 DEG C, soaking time 4h.
Embodiment 4
A kind of component and its mass percent of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material are as follows:
Carbon material 50%
Nanometer lead crystal grain 42%
Lead oxide 8%
Wherein: the carbon material is carbon nano-fiber.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, with embodiment 1, in which:
In (1) step, mixed solution A according to plumbi nitras quality (g): the volume (mL) of deionized water is 0.4:500
Proportional arrangement.
In (2) step, mixed solution B according to carbon material quality (g): the volume (mL) of mixed solution A be 1:500 ratio
Example configuration, is stirred 20 minutes.Wherein: the carbon material is carbon nano-fiber.
In (3) step, mixed solution C is according to aqueous slkali: the volume ratio of mixed solution B is the proportional arrangement of 1:50, stirring
22 minutes.Wherein: the aqueous slkali is NaHCO3Solution.
In (4) step, freeze-drying temperature is -78 DEG C, vacuum degree 4Pa, sublimation drying 22h.Wherein: described
Separation of solid and liquid be vacuum filtration, vacuum degree be -0.096MPa.
In (5) step, heating temperature is 500 DEG C, soaking time 3h.
Embodiment 5
A kind of component and its mass percent of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material are as follows:
Carbon material 40%
Nanometer lead crystal grain 51%
Lead oxide 9%
Wherein: the carbon material is graphite oxide.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, with embodiment 1, in which:
In (1) step, mixed solution A according to plumbi nitras quality (g): the volume (mL) of deionized water is 0.5:500
Proportional arrangement.
In (2) step, mixed solution B according to carbon material quality (g): the volume (mL) of mixed solution A be 1:500 ratio
Example configuration, is stirred 25 minutes.Wherein: the carbon material is graphite oxide.
In (3) step, mixed solution C is according to aqueous slkali: the volume ratio of mixed solution B is the proportional arrangement of 1:50, stirring
28 minutes.Wherein: the aqueous slkali is NaOH solution.
In (4) step, freeze-drying temperature is -80 DEG C, vacuum degree 3Pa, sublimation drying 23h.Wherein: described
Separation of solid and liquid be centrifuge separation, the revolving speed of centrifuge separation is 4000r/min.
In (5) step, heating temperature is 550 DEG C, soaking time 2h.
Embodiment 6
A kind of component and its mass percent of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material are as follows:
Carbon material 30%
Nanometer lead crystal grain 60%
Lead oxide 10%
Wherein: the carbon material is active carbon.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, with embodiment 1, in which:
In (1) step, mixed solution A according to plumbi nitras quality (g): the volume (mL) of deionized water is 0.5:500
Proportional arrangement.
In (2) step, mixed solution B according to carbon material quality (g): the volume (mL) of mixed solution A be 1:500 ratio
Example configuration, is stirred 26 minutes.Wherein: the carbon material is carbon nano-fiber.
In (3) step, mixed solution C is according to aqueous slkali: the volume ratio of mixed solution B is the proportional arrangement of 1:50, stirring
24 minutes.Wherein: the aqueous slkali is KOH solution.
In (4) step, freeze-drying temperature is -76 DEG C, vacuum degree 2Pa, and sublimation drying is for 24 hours.Wherein: described
Separation of solid and liquid be vacuum filtration, vacuum degree be -0.097MPa.
In (5) step, heating temperature is 600 DEG C, soaking time 3h.
Embodiment 7
A kind of component and its mass percent of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material are as follows:
Carbon material 20%
Nanometer lead crystal grain 75%
Lead oxide 5%
Wherein: the carbon material is carbon nano-fiber.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, with embodiment 1, in which:
In (1) step, mixed solution A according to plumbi nitras quality (g): the volume (mL) of deionized water is 0.55:500
Proportional arrangement.
In (2) step, mixed solution B according to carbon material quality (g): the volume (mL) of mixed solution A be 1:500 ratio
Example configuration, is stirred 28 minutes.Wherein: the carbon material is carbon nano-fiber.
In (3) step, mixed solution C is according to aqueous slkali: the volume ratio of mixed solution B is the proportional arrangement of 1:50, stirring
28 minutes.Wherein: the aqueous slkali is KOH solution.
In (4) step, freeze-drying temperature is -80 DEG C, vacuum degree 2.5Pa, and sublimation drying is for 24 hours.Wherein: institute
The separation of solid and liquid stated is centrifuge separation, centrifugal rotational speed 3700r/min.
In (5) step, heating temperature is 550 DEG C, soaking time 4h.
Embodiment 8
A kind of component and its mass percent of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material are as follows:
Carbon material 10%
Nanometer lead crystal grain 80%
Lead oxide 10%
Wherein: the carbon material is graphene nanometer sheet.
A kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, with embodiment 1, in which:
In (1) step, mixed solution A according to plumbi nitras quality (g): the volume (mL) of deionized water is 0.6:500
Proportional arrangement.
In (2) step, mixed solution B according to carbon material quality (g): the volume (mL) of mixed solution A be 1:500 ratio
Example configuration, is stirred 30 minutes.Wherein: the carbon material is carbon nano-fiber.
In (3) step, mixed solution C is according to aqueous slkali: the volume ratio of mixed solution B is the proportional arrangement of 1:50, stirring
30 minutes.Wherein: the aqueous slkali is NaOH solution.
In (4) step, freeze-drying temperature is -80 DEG C, vacuum degree 2Pa, and sublimation drying is for 24 hours.Wherein: described
Separation of solid and liquid be vacuum filtration, vacuum degree be -0.01MPa.
In (5) step, heating temperature is 600 DEG C, soaking time 3h.
Test result
Electronic Speculum is scanned to carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material that embodiment 1 is prepared
Characterization, as shown in Figure 1.
As shown in Figure 1, in carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, lead crystal grain/lead oxide grain
Diameter is 10~500nm, is equably supported on carbon material surface and interlayer, effectively prevents the reunion of lead particle, and carbon material
Also unobstructed electronics and heat transfer channel are provided to lead crystal grain and Nanometer sized lead oxide.Load the carbon of nanometer lead crystal grain and lead oxide
Material can be mixed preferably with lead active material, increased effective contact interface product of lead active material and Carbon Materials, given full play to
The advantage of the highly conductive and high capacitance of carbon material.And the lead introduced has high overpotential of hydrogen evolution, which is added lead
When carbon battery cathode, in the later period of charging, liberation of hydrogen problem can be effectively inhibited, charge-discharge performance is improved, extends the circulation of battery
Service life.
Claims (2)
1. a kind of composite material of carbon material in-situ deposition nanometer lead crystal grain/lead oxide, it is characterised in that the component of the material
And its mass percent are as follows:
Carbon material 10~80%
Nanometer lead crystal grain 80~15%
Lead oxide 10~5%
Wherein: the carbon material is carbon nanotube or active carbon or carbon nano-fiber or graphene nanometer sheet or graphite oxide,
Phosphorus content is at least 90% or more；The partial size of nanometer lead crystal grain is 30~500nm；The partial size of lead oxide is 10~300nm.
2. a kind of preparation method of carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material, it is characterised in that including such as
Lower step:
(1) according to the quality of soluble lead salt: the ratio between volume of deionized water is the ratio of 0.1~0.6g:500ml, will be solvable
Property lead salt is dissolved into deionized water, obtains mixed solution A after being sufficiently stirred；
Wherein: the dissolvable lead salt is plumbi nitras or lead acetate or lead sulfate；
(2) according to the quality of carbon material: the ratio between volume of mixed solution A is the ratio of 1g:500ml, and carbon material is evenly dispersed
It into mixed solution A, is mixed 10~30 minutes at room temperature, obtains the mixed solution B of carbon material and soluble lead salt；
Wherein: the carbon material is carbon nanotube or active carbon or carbon nano-fiber or graphene nanometer sheet or graphite oxide；
(3) according to mixed solution B: the volume ratio of aqueous slkali is the ratio of 1:50, and certain density aqueous slkali is slowly added into
Mixed solution B is mixed 10~30 minutes at room temperature, obtains mixed solution C；
Wherein: the aqueous slkali is KOH or NaOH or Na2CO3Or NaHCO3Or ammonium hydroxide, concentration 1mol/L；
(4) (3) resulting mixed solution C is separated by solid-liquid separation, is washed with one or both of deionized water and ethyl alcohol molten
Liquid washs repeatedly, until filtrate reaches neutral (i.e. pH reaches 7), the solids finally collected is placed in -50~-80 DEG C, vacuum
Degree is drying 4~24 hours under 1~10Pa, obtains carbon material in-situ deposition nanometer lead crystal grain/oxidation lead composite material forerunner
Body；
Wherein: the separation of solid and liquid is centrifuge separation or vacuum filtration, and the revolving speed of centrifuge separation is 2000~4000r/min,
The vacuum degree of vacuum filtration is -0.09~-0.1MPa；
(5) (4) resulting presoma is heated in inert gas 300~600 DEG C, and keeps the temperature 2~6 hours, be cooled to room
Carbon material in-situ deposition nanometer lead crystal grain/lead oxide composite material can be prepared after temperature.
Wherein: the inert gas is high-purity nitrogen or argon gas or helium.
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