CN103579616A - Graphene coated lead powder composite material and application thereof - Google Patents

Graphene coated lead powder composite material and application thereof Download PDF

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Publication number
CN103579616A
CN103579616A CN201310534798.3A CN201310534798A CN103579616A CN 103579616 A CN103579616 A CN 103579616A CN 201310534798 A CN201310534798 A CN 201310534798A CN 103579616 A CN103579616 A CN 103579616A
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China
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lead powder
composite
graphene
graphene coated
coated lead
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CN201310534798.3A
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Chinese (zh)
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郑华均
陈城勇
邸婧
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浙江工业大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a graphene coated lead powder composite material and an application thereof. A preparation method of graphene coated lead powder composite material comprises the following steps of: (1) modifying lead powder by using an aminosilane coupling agent so that the lead powder has positive charges on the surface, and then obtaining the modified lead powder with positive charges; (2) carrying out self-assembly of the modified lead powder obtained in the step (1) with oxidized graphene in deionized water A through electrostatic adsorption to obtain the oxidized graphene coated lead powder composite material; and (3) reducing the oxidized graphene coated lead powder composite material obtained in the step (2) into the graphene coated lead powder composite material. The graphene coated lead powder composite material can be used as the cathode material of a lead-carbon super battery. A polar plate made from the graphene coated lead powder composite material is good in mechanical strength; a battery made from the composite material as the cathode material is excellent in charge/discharge performance, power density, specific capacity and cycle life.

Description

A kind of graphene coated lead powder composite material and application thereof
Technical field
The present invention relates to a kind of graphene coated lead powder composite material making by electrostatic self-assembled method and as the application of plumbous carbon superbattery negative material.
Background technology
The development of more than 100 year of lead acid accumulator experience, the advantages such as the maturation that possesses skills, security performance is good, cost is low, stable performance and resource regeneration rate of recovery height, have all made great contribution in many application aspect.Development along with electric automobile industry, the charge-discharge performance of battery and cycle life have been had to the lifting of larger requirement, and lead-acid battery power density is not high, after recycling for a long time, especially under partial state of charge during high-multiplying power discharge, easily there is irreversible " sulfation " in negative pole, causes its cycle life far below its potential life-span.So will carry out modification to lead-acid battery, improve its power density, charge-discharge performance and cycle performance.
Ultracapacitor is a kind of novel energy storage device, the feature such as there is high power density, fast charging and discharging, have extended cycle life, but the relative battery of its energy density is lower, so by the use that is together in parallel of lead-acid battery and ultracapacitor, both learn from other's strong points to offset one's weaknesses, make up shortcoming separately, performance advantage each other.
Mainly contain at present two kinds of method of modifying: a kind of superbattery that is called, ultracapacitor and lead-acid battery are carried out in parallel, ultracapacitor carbon negative pole and lead-acid battery negative pole are in parallel, and the advantage of double electric layer capacitor is fused in lead-acid battery.In patent CN102064319A, disclose a patent, in negative terminal surface, applied one deck carbon paste, made negative plate.Another kind is called plumbous carbon battery, and material with carbon element is directly mixed with lead powder, makes pole plate.Material with carbon element can improve the dispersiveness of lead powder on the one hand, and in the process discharging and recharging, material with carbon element has played a kind of effect of buffer current to pole plate simultaneously, in recycling, can play the effect that suppresses sulfation in addition.Patent CN101969149A discloses some material with carbon elements has been joined to the method for mixing in lead powder, and has added liberation of hydrogen inhibitor, alleviates material with carbon element and adds the violent evolving hydrogen reaction causing.In recent years, due to conductivity and the superhigh specific surface area of Graphene excellence, many researchers were attempting Graphene for lead-acid battery.In patent CN102760868A, disclose grapheme material has directly been mixed with lead powder, made the negative plate that contains grapheme material.But because Graphene and plumbous density differ greatly, cause both not mix equably, and by the mode of mechanical mixture, plumbous less with effective contact interface of material with carbon element, can not give full play to the electricity of carbon and lead and electric capacity advantage.In patent CN102881866A, disclose the method deposit lead on Graphene by electro-deposition, obtained plumbous graphene composite material, and mix with lead powder, made negative plate.Although by modified graphene, improved the uniformity that both mix, effective contact interface of Graphene and plumbous active material is less, and both associativities are not good.In CN1022912174A, disclose the method by electro-deposition, prepared Graphene and plumbous composite material, and using this material as negative electrode active material, make negative plate.This invention has well solved Graphene and plumbous associativity problem, has also improved both effective contacts area, but this invention complex process in early stage is difficult for industrialization, and environmental pollution is also relatively large.
As can be seen here, must improve associativity, the mixture homogeneity of material with carbon element and lead powder, and both effective contacts area, select the material with carbon element of high conductivity and high capacitance, in conjunction with above-mentioned several method of modifying to lead-acid battery simultaneously.The present invention adopts electrostatic self-assembled legal system for graphene coated lead powder composite material, not only improved the associativity of Graphene and lead powder, and can make graphene uniform and be coated on polar board surface and disperse wherein equably, be conducive to form carbonaceous conductive network between lead powder, both effective contacts area have been increased greatly, impel the conversion rate between lead and lead sulfate, thereby stoped the accumulation of bulky grain lead sulfate.In addition, the liberation of hydrogen inhibitor adding can finely must suppress Graphene and add the evolving hydrogen reaction causing.The plumbous carbon superbattery of assembling, has not only improved charge-discharge performance, has improved power density, and has promoted discharge capacity of the cell to a great extent, has extended charge and discharge circulation life.
Summary of the invention
The object of this invention is to provide a kind of graphene coated lead powder composite material and as the application of plumbous carbon superbattery negative material, the pole plate mechanical strength that adopts described graphene coated lead powder composite material to make is good, can effectively guarantee the uniformity that Graphene mixes with lead powder simultaneously, and greatly having improved Graphene and the effective contact area of lead powder, the battery that this composite material makes as negative material of usining has good charge-discharge performance, power density, specific capacity and cycle life.
For achieving the above object, the present invention adopts following technical scheme:
A lead powder composite material, its preparation method comprises the steps:
(1) adopt amino silicane coupling agent to carry out modification to lead powder, make positive charge on lead powder surface band, obtain the modification lead powder of positively charged;
(2) make modification lead powder and graphene oxide that step (1) obtains by Electrostatic Absorption, carry out self assembly in deionized water A, obtain the composite material of the coated lead powder of graphene oxide;
(3) composite material of the coated lead powder of graphene oxide step (2) being made is reduced into graphene coated lead powder composite material;
The mass ratio that feeds intake of described amino silicane coupling agent, lead powder, graphene oxide, deionized water A is 0.05~1:20~100:0.2~1:100~1000, is preferably 0.1~0.8:30~60:0.3~0.6:200~600.
Further, described step (3) can be by adding reducing agent or high temperature to make the composite material of the coated lead powder of graphene oxide be reduced into graphene coated lead powder composite material.It is one of following that applicable reducing agent can be selected from: hydrazine hydrate, sodium borohydride, glucose, natrium citricum, ethylenediamine, ascorbic acid, hydroiodic acid, Cys; The mass ratio that feeds intake of described reducing agent and amino silicane coupling agent, lead powder, graphene oxide, deionized water A is 0.5~10:0.05~1:20~100:0.2~1:100~1000, is preferably 1~8:0.1~0.8:30~60:0.3~0.6:200~600.When adopting high temperature reduction, under inert protective gas atmosphere, to carry out, described inert protective gas is nitrogen or inert gas, preferably 200~600 ℃ of reduction temperatures, isothermal reaction 0.5~6h.
Further, described amino silicane coupling agent is selected from one of following: gamma-aminopropyl-triethoxy-silane (KH550 or A1100), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792 or A1120), N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane (KBM-602), N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-γ-aminopropyl methyldiethoxysilane, aminoethyl aminoethyl aminopropyl trimethoxysilane (A-1130), polyamino alkyltrialkoxysilaneand (Y-5691).
Further, described lead powder is conventional technical grade product, and particle diameter is at 0.1~20 μ m, degree of oxidation of lead powder: 70~80%.
Further, described graphene oxide adopts hummer or the preparation of hummer improved method.
Graphene coated lead powder composite material described in the present invention also provides is as the application of the negative material of plumbous carbon superbattery, and the preparation method of plumbous carbon superbattery specifically comprises the steps:
(1) preparation of plumbous carbon superbattery cathode lead plaster:
1. raw material and weight portion proportioning thereof are as follows:
90~100 parts, graphene coated lead powder composite material, 0.05~2 part, barium sulfate, 5~20 parts, the sulfuric acid that density is 1.15g/ml, 0.01~0.5 part, short fiber, 0.1~5 part of conductive agent, 0.05~2 part, liberation of hydrogen inhibitor, 10~20 parts of deionized waters; Wherein said conductive agent is a kind of in electrically conductive graphite, acetylene black, carbon black etc.; Wherein said liberation of hydrogen inhibitor is one or more in indium oxide, bismuth oxide, zinc oxide, barium stearate etc.;
2. according to said ratio, get raw material, first graphene coated lead powder composite material, barium sulfate, short fiber, conductive agent and liberation of hydrogen inhibitor are poured in container, each component is fully mixed, then adding deionized water and density is the sulfuric acid of 1.15g/ml, controlling temperature carries out and cream under stirring condition at 45~55 ℃, obtain plumbous carbon superbattery cathode lead plaster, and control apparent density of lead paste at 3.8~4.5g/ml;
(2) plumbous carbon superbattery cathode lead plaster step (1) being obtained is coated on grid equably, and flood 5~10s in the sulfuric acid that is 1.15g/ml in density, then under the condition that pole plate to be placed in to temperature and to be 45~55 ℃, relative humidity be 90~100%, solidify 12~48h, pole plate is put into 50~75 ℃ again, dry 18~48h, obtains green plate;
(3) green plate being cured is carried out to outer changing into, dry after, obtain ripe pole plate, and dress up battery with the modal sets of " two positive negative ".
The present invention dresses up pole plate after battery with the modal sets of " two positive negative ", can adopt following method to carry out the test of initial capacity: battery is full of after electricity, with the electric current of 750mA, it is discharged, cut-ff voltage is 1.75V; Adopt following method to carry out the test of charge-discharge performance: respectively with 500,700,750mA current charges is to voltage 2.42V, constant voltage 2.42V, time 2h, after standing 5min, respectively with 500,700,750mA current discharge, cut-ff voltage 1.75V; Adopt following method to carry out the test of charge-discharge performance: with 500mA current charges to voltage 2.42V, constant voltage 2.42V, time 2h, after standing 5min, with 500mA current discharge, cut-ff voltage 1.75V, be a circulation, carry out 50 loop test comparisons.
Compared with prior art, beneficial effect of the present invention is:
A) lead powder that the present invention adopts is processed through graphene coated, by amino coupling agent, lead powder is processed, make its lotus that becomes positively charged, utilize electrostatic self-assembled method simple, obtain rapidly graphene coated lead powder composite material, make graphene uniform and be coated on lead powder surface, improved the uniformity of the dispersiveness of Graphene between lead powder and both mixing, simultaneously, the Graphene being coated on lead powder has the effect of buffer current to pole plate, the graphene conductive network configuration forming between lead powder, improved widely the electric conductivity of material, can improve lead sulfate and plumbous transformation efficiency, suppressing well oarse-grained lead sulfate occurs.With the battery of the present invention's assembling, graphene coated is surperficial at lead, make carbon negative pole and plumbous negative pole carry out " inside also ", bring into play better capacitive character and battery, form two property negative poles, there is the feature of superbattery.In addition, in charging process, the membership that adds of material with carbon element makes battery shift to an earlier date liberation of hydrogen, and the liberation of hydrogen inhibitor adding is mainly to reduce the liberation of hydrogen of battery in charging process, the performance that so just can guarantee Graphene is brought into play, suppress the dry of electrolyte, extend the life of a cell, so liberation of hydrogen inhibitor is the key factor of plumbous carbon superbattery.
B) composite material of graphene coated lead powder of the present invention is compared with the material that Graphene is directly mixed to form with lead powder, there is stronger adhesion, therefore the pole plate that adopts the composite material of graphene coated lead powder of the present invention to make, there is extraordinary mechanical strength, and greatly improved effective contact area of Graphene and lead powder.
C) specific discharge capacity, quality that adopts the plumbous carbon superbattery that the inventive method makes is all significantly improved than the utilance of power, lead powder and charge-discharge performance and cycle performance.
Accompanying drawing explanation
Fig. 1 is the XRD figure of graphene coated lead powder;
Fig. 2 is the SEM figure of graphene coated lead powder;
Fig. 3 is the TEM figure of graphene coated lead powder;
Fig. 4 is the battery initial capacity figure of embodiment 1 and comparative example 1;
Fig. 5 is that the battery 750mA of embodiment 1 and comparative example 1 charges and discharge electrograph;
Fig. 6 is 50 cycle performance figure of battery of embodiment 1 and comparative example 1.
Embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited to this: comparative example 1
Business lead powder (Tianjin Zhong Tianpengbo metal material Co., Ltd) is directly mixed with other raw materials, it is not carried out to the coated processing of carbon, by the weight proportion of following material, make lead-acid battery: lead powder 98, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 1.5, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 5~10s, at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the chemical property of battery is as shown in curve B lank in Fig. 4,5,6, and wherein Fig. 4 is battery initial capacity figure, and Fig. 5 is that battery 750mA charges and discharge electrograph, and Fig. 6 is 50 cycle performance figure of battery.
Embodiment 1
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.1g amino silicane coupling agent KH550, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KH550 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 300ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 300ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is joined in the aqueous solution that contains 2g glucose, drip 2ml ammoniacal liquor, at 90 ℃, stir 2h, suction filtration, washing, to neutral, obtain the composite material of the graphene coated lead powder of light/dark balance after being dried, grinding.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.2 part, short fiber, 0.3 part, barium sulfate, 0.6 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, under stirring condition, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 10s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, chemical property is as shown in curve GNSPb in Fig. 4,5,6.The initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 31.4%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 23.3% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.83 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 2
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.1g amino silicane coupling agent KH550, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KH550 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 400ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 350ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is joined in the aqueous solution that contains 4g glucose, drip 2ml ammoniacal liquor, at 90 ℃, stir 2h, suction filtration, washing, to neutral, obtain the composite material of the graphene coated lead powder of light/dark balance after being dried, grinding.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.3 part, short fiber, 0.3 part, barium sulfate, 0.5 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, under stirring condition, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 10s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 22.7%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 30.3% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.67 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 3
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.2g amino silicane coupling agent KH570, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KH570 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 500ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 300ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is joined in the aqueous solution that contains 4g natrium citricum, drip 2ml ammoniacal liquor, at 90 ℃, stir 2h, suction filtration, washing, to neutral, obtain the composite material of the graphene coated lead powder of light/dark balance after being dried, grinding.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.2 part, short fiber, 0.3 part, barium sulfate, 0.6 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 10s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 21.7%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 29.3% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.47 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 4
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.5g amino silicane coupling agent KH792, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KH792 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 400ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 300ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is joined in the aqueous solution that contains 2g natrium citricum, drip 2ml ammoniacal liquor, at 90 ℃, stir 2h, suction filtration, washing, to neutral, obtain the composite material of the graphene coated lead powder of light/dark balance after being dried, grinding.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.2 part, short fiber, 0.3 part, barium sulfate, 0.6 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 10s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 29.7%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 32.3% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.73 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 5
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.5g amino silicane coupling agent KBM-602, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KBM-602 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 500ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 300ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is joined in the aqueous solution that contains 2g glucose, drip 2ml ammoniacal liquor, at 90 ℃, stir 2h, suction filtration, washing, to neutral, obtain the composite material of the graphene coated lead powder of light/dark balance after being dried, grinding.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.2 part, short fiber, 0.3 part, barium sulfate, 0.6 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, under stirring condition, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 5s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 28.7%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 29.3% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.37 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 6
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.5g amino silicane coupling agent KH550, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KH550 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 500ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 300ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is joined in the aqueous solution that contains 1g sodium borohydride, drip 2ml ammoniacal liquor, at 90 ℃, stir 2h, suction filtration, washing, to neutral, obtain the composite material of the graphene coated lead powder of light/dark balance after being dried, grinding.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.2 part, short fiber, 0.3 part, barium sulfate, 0.6 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, under stirring condition, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 10s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 30.7%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 33.8% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.87 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 7
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.3g amino silicane coupling agent KH550, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KH550 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 500ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 300ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is joined in the aqueous solution that contains 2g sodium borohydride, drip 2ml ammoniacal liquor, at 90 ℃, stir 2h, suction filtration, washing, to neutral, obtain the composite material of the graphene coated lead powder of light/dark balance after being dried, grinding.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.2 part, short fiber, 0.3 part, barium sulfate, 0.6 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 10s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 20.7%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 29.3% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.52 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 8
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.4g amino silicane coupling agent KH550, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KH550 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 450ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 300ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of thermal reduction 6h, after grinding, obtain the composite material of lead powder of the graphene coated of light/dark balance.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.2 part, short fiber, 0.3 part, barium sulfate, 0.6 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 10s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 23.7%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 26.3% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.34 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 9
First 40g business lead powder, 200ml ethanol and 4ml deionized water are mixed to 10min under high-speed stirred, then add 0.5g amino silicane coupling agent KH570, at 60 ℃, add thermal agitation 10h, suction filtration, wash away not the KH570 with lead powder coupling, dry, to obtain modification after grinding positively charged lead powder.
Getting concentration is the graphite oxide aqueous solution 500ml of 1mg/ml, and ultrasonic 1h makes it dispersed.By the lead powder after above-mentioned modification, join in the deionized water of 100ml, stir 10min, then slowly add 300ml graphite oxide aqueous solution, concussion is stirred, after standing 30min, can see the obvious layering of solution, upper strata color is thin out, slowly clarification, the sediment color of lower floor slowly becomes sepia, and suction filtration, washing, dry, grinding, obtain the composite material that graphene oxide is coated lead powder.This composite material is put into tube furnace, under nitrogen atmosphere, carry out 300 ℃ of thermal reduction 5h, after grinding, obtain the composite material of lead powder of the graphene coated of light/dark balance.
By the weight proportion of following material, make plumbous carbon superbattery: 98.5 parts, graphene coated lead powder composite material, 0.2 part, short fiber, 0.3 part, barium sulfate, 0.6 part of electrically conductive graphite, 0.4 part of indium oxide, after mixing, add above-mentioned raw materials gross mass 18%, the deionized water of the sulfuric acid of 1.15g/ml and above-mentioned raw materials gross mass 12%, at 50 ℃, carry out and cream, obtain apparent density at the lead plaster of 3.8~4.5g/ml, applied after pole plate, in the sulfuric acid that is 1.15g/ml in density, flood 10s, then at 50 ℃, under the condition of relative humidity 90~98%, solidify 24 hours, then at 65 ℃, be dried 24 hours, obtain raw negative plate, by the method (sulfuric acid at 1.05g/ml changes into) changing into, obtain ripe negative plate outward at home and abroad.Adopt this negative plate and PbO 2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 26.9%; Carry out equally 750mA electric current charge-discharge test, the discharge capacity of battery also has 30.1% lifting; Aspect cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.66 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obvious change large, and capacity also has lifting, the lead powder of graphene coated prepared by the present invention is described, in battery charge and discharge process, Graphene and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.

Claims (8)

1. a graphene coated lead powder composite material, its preparation method comprises the steps:
(1) adopt amino silicane coupling agent to carry out modification to lead powder, make positive charge on lead powder surface band, obtain the modification lead powder of positively charged;
(2) make modification lead powder and graphene oxide that step (1) obtains by Electrostatic Absorption, carry out self assembly in deionized water A, obtain the composite material of the coated lead powder of graphene oxide;
(3) composite material of the coated lead powder of graphene oxide step (2) being made is reduced into graphene coated lead powder composite material;
The mass ratio that feeds intake of described amino silicane coupling agent, lead powder, graphene oxide, deionized water A is 0.05~1:20~100:0.2~1:100~1000.
2. graphene coated lead powder composite material as claimed in claim 1, it is characterized in that: in step (3), use reducing agent that the composite material of the coated lead powder of graphene oxide is reduced into graphene coated lead powder composite material, it is one of following that described reducing agent is selected from: hydrazine hydrate, sodium borohydride, glucose, natrium citricum, ethylenediamine, ascorbic acid, hydroiodic acid, Cys.
3. graphene coated lead powder composite material as claimed in claim 2, is characterized in that: the mass ratio that feeds intake of described reducing agent and amino silicane coupling agent, lead powder, graphene oxide, deionized water A is 0.5~10:0.05~1:20~100:0.2~1:100~1000.
4. graphene coated lead powder composite material as claimed in claim 3, is characterized in that: the mass ratio that feeds intake of described reducing agent and amino silicane coupling agent, lead powder, graphene oxide, deionized water A is 1~8:0.1~0.8:30~60:0.3~0.6:200~600.
5. graphene coated lead powder composite material as claimed in claim 1; it is characterized in that: described step (3) makes the composite material of the coated lead powder of graphene oxide be reduced into graphene coated lead powder composite material by high temperature reduction; described high temperature reduction carries out under inert protective gas atmosphere; reduction temperature is at 200~600 ℃, isothermal reaction 0.5~6h.
6. the graphene coated lead powder composite material as described in one of claim 1~5, is characterized in that described amino silicane coupling agent is selected from one of following: gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-γ-aminopropyl methyldiethoxysilane, aminoethyl aminoethyl aminopropyl trimethoxysilane, polyamino alkyltrialkoxysilaneand.
7. graphene coated lead powder composite material as claimed in claim 1 is as the application of the negative material of plumbous carbon superbattery.
8. application as claimed in claim 7, is characterized in that the preparation method of described plumbous carbon superbattery specifically comprises the steps:
(1) preparation of plumbous carbon superbattery cathode lead plaster:
1. raw material and weight portion proportioning thereof are as follows:
90~100 parts, graphene coated lead powder composite material, 0.05~2 part, barium sulfate, 5~20 parts, the sulfuric acid that density is 1.15g/ml, 0.01~0.5 part, short fiber, 0.1~5 part of conductive agent, 0.05~2 part, liberation of hydrogen inhibitor, 10~20 parts of deionized waters; Wherein said conductive agent is a kind of in electrically conductive graphite, acetylene black, carbon black; Wherein said liberation of hydrogen inhibitor is one or more in indium oxide, bismuth oxide, zinc oxide, barium stearate;
2. according to said ratio, get raw material, first graphene coated lead powder composite material, barium sulfate, short fiber, conductive agent and liberation of hydrogen inhibitor are poured in container, each component is fully mixed, then adding deionized water and density is the sulfuric acid of 1.15g/ml, controlling temperature carries out and cream under stirring condition at 45~55 ℃, obtain plumbous carbon superbattery cathode lead plaster, and control apparent density of lead paste at 3.8~4.5g/ml;
(2) plumbous carbon superbattery cathode lead plaster step (1) being obtained is coated on grid equably, and flood 5~10s in the sulfuric acid that is 1.15g/ml in density, then under the condition that pole plate to be placed in to temperature and to be 45~55 ℃, relative humidity be 90~100%, solidify 12~48h, again by pole plate in 50~75 ℃ of dry 12~48h, obtain green plate;
(3) green plate being cured is carried out to outer changing into, dry after, obtain ripe pole plate, and dress up battery with the modal sets of " two positive negative ".
CN201310534798.3A 2013-10-31 2013-10-31 Graphene coated lead powder composite material and application thereof CN103579616A (en)

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