CN102683708A - Negative plate of battery, preparation method thereof and battery comprising negative plate - Google Patents
Negative plate of battery, preparation method thereof and battery comprising negative plate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011149 active material Substances 0.000 claims abstract description 27
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000011505 plaster Substances 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007767 bonding agent Substances 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 8
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004021 humic acid Substances 0.000 claims description 7
- 229920005610 lignin Polymers 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 5
- 230000005764 inhibitory process Effects 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims 1
- 229920006184 cellulose methylcellulose Polymers 0.000 claims 1
- 229920003048 styrene butadiene rubber Polymers 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- -1 sulfoxide titanium oxide Chemical class 0.000 abstract description 2
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 23
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- SMBGWMJTOOLQHN-UHFFFAOYSA-N lead;sulfuric acid Chemical compound [Pb].OS(O)(=O)=O SMBGWMJTOOLQHN-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
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- 238000001035 drying Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- 239000010936 titanium Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a negative plate of a battery, a preparation method thereof and the battery comprising the negative plate. The negative plate is composed of a plate grid and a negative pole material coated on the plate grid, and the negative pole material comprises a battery active material, a capacitor material as well as a conductive steric hindrance agent; the battery active material comprises 100 parts by weight of lead powder, 0.6-2.0 parts by weight of barium sulfate and 0.1-0.5 part by weight of short fiber, and the capacitor material comprises 0.1-10 parts by weight of active carbon; and the additive amount of the electric conduction steric hindrance agent is 0.1-5.0 in parts by weight, and the conductive steric hindrance agent comprises Magneli mutual sulfoxide titanium oxide and/or plumbous acid barium. The raw material of the negative plate of the battery provided by the invention can be used for postponing a negative board sulphate phenomenon through combining the three parts, the cold-starting property is markedly improved, and the heavy-current charge-discharge property is optimized.
Description
Technical field
The present invention relates to field of batteries, in particular to a kind of negative plate, its preparation method of battery and comprise its battery.
Background technology
In recent years, along with the shortage and the price of petroleum resources rises steadily, the research and development of electro-motive vehicle and use become the most popular now topic.And the bottleneck that restricts electric driving cars development is exactly the power that is powered vehicle a---storage battery.Can lithium ion battery, metal-hydrogen nickel battery, lead accumulator or the like be arranged as the storage battery of powered vehicle at present, wherein technology maturation, moderate lead accumulator occupy absolute ratio, account for more than 90% of the battery of electric vehicle market share.But lead-acid battery cycle life is short, high-rate performance is poor, and problems such as cold cranking capacity difference are denounced by people always.The cost of material of current lead-acid battery and the environmental protection cost greatly promotes and other new varieties batteries emerge in an endless stream is constantly impacting overlord's throne of lead-acid battery, the huge crisis of original lead-acid battery industry faces.
Initial plumbous carbon superbattery is to adopt the mode of lead-acid battery and ultracapacitor parallel connection outside to combine.The cycle life that the plumbous carbon superbattery of " outward also " can prolong battery; Improve high-rate performance, and certain lifting has also been arranged aspect cold-starting, but this battery need increase circuit control system; This has not only increased volume of battery, and has increased battery cost.The battery that the most important thing is this structure is limited to performance boost, does not reach the height of people's expection fully." also interior " becomes the developing direction of plumbous carbon superbattery.In this case, the superbattery notion that CSIRO proposes can ideally solve above problem.Plumbous carbon super accumulator is that ultracapacitor is evolved to " also interior " with the parallelly connected use (can claim " also " outward) of plumbic acid, exactly the high-specific-power of double electric layer capacitor, long-life advantage is fused in the lead-acid battery.So not only can simplify circuit, improve specific energy, and reduce total cost, and aspect raising power, the extending battery life more excellent performance arranged outward than " also ".It is in growing electric bicycle of China and the electric automobile that starting, with producing huge economic benefit and social benefit.
Yet plumbous carbon superbattery still has a lot of technological difficulties not solve fully as yet as a kind of new ideas battery, wherein the most important thing is the quality problems of negative plate.Since interior and mainly be meant the negative plate of lead-acid battery and the negative plate of ultracapacitor are effectively combined, so the performance of negative plate is directly determining the quality of battery.Now the main R&D direction of each company has: 1) negative plate of battery and electric capacity are born plate and be together in parallel and be assembled in the battery; 2) diverse location that lead plaster and carbon paste is coated in negative electrode grid is made negative plate; 3) carbon paste is coated in the lead plaster outside.But all there is shortcoming in above-mentioned several kinds of directions, and in first kind of scheme, additional electric capacity is born plate, not only can increase the weight of battery, and under the situation of constancy of volume, also can reduce the amount of battery active material; Second kind of scheme is very high to the requirement of grid, because carbon paste is softer, can't be as lead plaster attached on the common batteries grid, and also the required thickness of carbon paste and lead plaster differs, and also is one of defective of this scheme; In the third scheme, the thickness of carbon paste is difficult to be controlled at lead plaster and applies evenly, and the contact-making surface of carbon paste and lead plaster may make the capacitive property of carbon paste get a desired effect.
Summary of the invention
The present invention aims to provide a kind of negative plate, its preparation method of battery and comprises its battery, and battery cycle life is short in the prior art, the charging interval is long and the problem of cold starting performance difference to solve.
To achieve these goals, according to an aspect of the present invention, a kind of negative plate of battery is provided.This negative plate is made up of grid and the negative material of full-filling on grid; Negative material comprises cell active materials, capacitance material; And conduction steric hindrance agent; Wherein, cell active materials comprises the lead powder of 100 weight portions, the barium sulfate of 0.6～2.0 weight portion, and the short fiber of 0.1～0.5 weight portion; Capacitance material comprises the active carbon of 0.1～10 weight portion; And the addition of conduction steric hindrance agent is 0.1～5.0 weight portion, and the agent of conduction steric hindrance comprises mutually inferior titanium oxide of Magneli and/or plumbic acid barium.
Further, the doped chemical in the mutually inferior titanium oxide of Magneli is selected from one or more elements in the group of being made up of Nb, Co, V.
Further, capacitance material also comprises one or more in the group of being made up of graphite, carbon fiber, CNT.
Further, capacitance material also comprises the agent of inhibition liberation of hydrogen, and the agent of inhibition liberation of hydrogen is selected from one or more in the group of being made up of oxide, hydroxide or the sulfate of lead, zinc, silver, bismuth, and the addition that suppresses the liberation of hydrogen agent is 0.01～1.0 weight portion.
Further, capacitance material also comprises bonding agent, and bonding agent is selected from one or more in the group of being made up of CMC, PTFE, PVDF, SBR, and the addition of bonding agent is 0～1.0 weight portion.
Further, cell active materials also comprises and is selected from the group of being made up of lignin, humic acid, acetylene black one or more.
Further, negative material comprises the raw material of following weight portion: lead powder 100 weight portions, barium sulfate 1.2 weight portions; Short fiber 0.2 weight portion, lignin 0.3 weight portion, humic acid 0.15 weight portion; Active carbon 2 weight portions, acetylene black 0.2 weight portion, and mutually inferior titanium oxide 3 weight portions of Magneli.
According to another aspect of the present invention, a kind of battery is provided.This battery comprises above-mentioned negative plate.
Further, battery is plumbous carbon superbattery.
A kind of preparation method of negative plate is provided according to a further aspect of the invention.This method may further comprise the steps: 1) cell active materials, capacitance material and the agent of conduction steric hindrance are mixed, add entry and sulfuric acid solution then, make the GND lead plaster; 2) the GND lead plaster is filled on grid, under 50～80 ℃, 95% above relative humidity, be cured, obtain negative pole and give birth to plate; 3) negative pole is given birth to the negative plate that plate carries out obtaining after the chemical synthesis technology battery.
Because the negative plate raw material of battery of the present invention is made up of cell active materials, capacitance material and conduction steric hindrance agent three parts, wherein, the major function of cell active materials provides the continuous discharge capacity; The major function of capacitance material is in the large current density electric process, electric double layer capacitance to be provided, and suppresses and the formation of the fine and close sulfuric acid lead layer in top layer of plumbous negative pole when alleviating high current charge-discharge, delays negative pole useful life, and improves its high-rate performance; The agent of conduction steric hindrance, the inferior titanium oxide (Ti that promptly has the Magneli phase
xO
2x-1) and/or the major function of plumbic acid barium be to be filled in that the aperture that makes electrode in the porous electrode reduces and porosity increases; Make the lead sulfate that generates in the plumbous negative discharge process when crystallization, produce steric hindrance; Suppressing the lead sulfate crystal grows up; Therefore suppress irreversible sulfuration effectively, improved the charge acceptance and the cycle life of electrode; Simultaneously because it has the conductivity near metal, add large current discharging capability, charge acceptance, the low temperature discharge ability that can improve electrode behind the negative pole to.The negative plate raw material of battery of the present invention is owing to the combination of above-mentioned three parts has delayed negative plate sulfation phenomenon, significantly improves cold starting performance, optimized high rate during charging-discharging.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the characteristic among the embodiment among the present invention can make up each other.To combine embodiment to specify the present invention below.
A kind of typical embodiment according to the present invention provides a kind of negative plate of battery.This negative plate is made up of grid and the negative material of full-filling on grid; Negative material comprises cell active materials, capacitance material and the agent of conduction steric hindrance; Wherein, cell active materials comprises the lead powder of 100 weight portions, the barium sulfate of 0.6～2.0 weight portion and the short fiber of 0.1～0.5 weight portion; Capacitance material comprises the active carbon of 0.1～10 weight portion; And the addition of conduction steric hindrance agent is 0.1～5.0 weight portion, and the agent of conduction steric hindrance comprises mutually inferior titanium oxide of Magneli and/or plumbic acid barium.
Because the negative plate raw material of battery of the present invention is made up of cell active materials, capacitance material and conduction steric hindrance agent three parts, wherein, the major function of battery activated carbon material provides the continuous discharge capacity; The major function that capacitance material is lived is in the large current density electric process, electric double layer capacitance to be provided, and suppresses and the formation of the fine and close sulfuric acid lead layer in top layer of plumbous negative pole when alleviating high current charge-discharge, delays negative pole useful life, and improves its high-rate performance; The agent of conduction steric hindrance, the inferior titanium oxide (Ti that promptly has the Magneli phase
xO
2x-1) and/or the major function of plumbic acid barium be to be filled in that the aperture that makes electrode in the porous electrode reduces and porosity increases; Make the lead sulfate that generates in the plumbous negative discharge process when crystallization, produce steric hindrance; Suppressing the lead sulfate crystal grows up; Therefore suppress irreversible sulfuration effectively, improved the charge acceptance of electrode; Simultaneously because it has the conductivity near metal, add large current discharging capability, charge acceptance, the low temperature discharge ability that can improve electrode behind the negative pole to.The negative plate raw material of battery of the present invention is owing to the combination of above-mentioned three parts has delayed negative plate sulfation phenomenon (raising battery useful life), significantly improves cold starting performance, optimized high rate during charging-discharging (reduce the charging interval and also improve the power of battery).
Wherein, inferior titanium oxide or its doping oxide can use separately, also can mix use with plumbic acid barium, also can be that plumbic acid barium uses separately, serve as the agent of conduction steric hindrance.
The battery activated carbon material mainly is a lead powder; It changes into the back and forms the lead sponge negative electrode active material; This battery activated carbon material also comprises the improved additive of plumbous negative pole performance such as barium sulfate, short fiber; Preferably, can also add being selected from the group of forming by lignin, humic acid, acetylene black one or more, to improve lead sponge continuous discharge capacity.Wherein, the addition of free lignin can can be 0.05～0.6 weight portion at the addition of 0.1～0.6 weight portion, acetylene black at the addition of 0.1～0.6 weight portion, humic acid;
The material, liberation of hydrogen inhibitor, bonding agent etc. that can add a certain amount of high conductivity in the capacitance material active carbon are to improve Properties of Activated Carbon.Preferably; Capacitance material also comprises one or more in the group of being made up of graphite, carbon fiber, CNT; Wherein, The addition of graphite is that the addition of 0～5 weight portion, carbon fiber is that the addition of 0～5 weight portion, CNT is 0～5 weight portion, to improve the electric conductivity of active carbon.The liberation of hydrogen inhibitor is selected from one or more in the group of being made up of the oxide of lead, zinc, silver, bismuth, hydroxide or sulfate.After active carbon adds negative pole to; Because the overpotential of hydrogen evolution of active carbon is lower than the overpotential of hydrogen evolution of plumbous negative pole; So that battery easy liberation of hydrogen decomposition water in charging process causes dry inefficacy of battery and lead sulfate not to be converted into lead fully and undercharge; Change the surface nature of active carbon through adding certain metal ion, improve the overpotential of hydrogen evolution of activated carbon surface, suppress and alleviate the hydrogen-separating quantity of active carbon in the negative pole charging process.Its addition is more than 0.01 weight fraction, and preferred optimum content is in 0.01～0.1 weight fraction.Bonding agent is selected from one or more in the group of being made up of CMC (carboxymethyl cellulose), PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), SBR (butadiene-styrene rubber); The addition of bonding agent is 0～1.0 weight portion; So that capacitance material has good adhesive strength, solve the problem of the easy softening and shedding of cell active materials effectively.
A kind of typical embodiment according to the present invention, doped chemical is selected from one or more elements in the group of being made up of Nb, Co, V in the mutually inferior titanium oxide of conduction steric hindrance agent Magneli.That is to say to have the inferior titanium oxide of Magneli phase, can mix, replace the Ti in the lattice, thereby make inferior titanium oxide conductivity higher with Magneli phase with Nb, Co, V, Nb particularly, effect is best.With Nb is instance, and the inferior titanium oxide of the Magneli phase after the doping can be used chemical formula Ti
xNb
yO
2 (x+y)-1Expression.The inferior titanium oxide (Ti of conduction steric hindrance agent with Magneli phase
xO
2x-1) and doping oxide, the wherein Ti of x=4
4O
7Suitable with the conductivity of graphite, its conductivity is 2.5 times of graphite.Inferior titanium oxide is used for plumbous negative pole and also has following characteristics: overpotential of hydrogen evolution high (being higher than active carbon, acetylene black, graphite), be insoluble to soda acid, in the negative reduction potential scope of lead, can be reduced.The major function of inferior titanium oxide component in negative pole is; To have certain grain size distribution inferior titanium oxide and lead powder, active carbon is mixed make electrode after; Inferior titanium oxide is filled in the aperture that makes electrode in the porous electrode to be reduced and the porosity increase, makes the lead sulfate that generates in the plumbous negative discharge process when crystallization, produce steric hindrance, suppresses the lead sulfate crystal and grows up; Therefore suppress irreversible sulfuration effectively, improved the charge acceptance of electrode; Simultaneously because it has the conductivity near metal, add large current discharging capability, charge acceptance, the low temperature discharge ability that can improve electrode behind the negative pole to.
Preferably, negative material comprises the raw material of following weight portion: lead powder 100 weight portions, barium sulfate 1.2 weight portions; Short fiber 0.2 weight portion, lignin 0.3 weight portion, humic acid 0.15 weight portion; Active carbon 2 weight portions, acetylene black 0.2 weight portion, and inferior titanium oxide 3 weight portions.
A kind of typical embodiment according to the present invention provides a kind of battery.This battery comprises above-mentioned negative plate.Positive plate can adopt the positive plate manufacture craft of traditional lead acid batteries to accomplish.Can be internalized into and obtain the finished product battery with being assembled into battery with green plate, also can be earlier the green plate alienation being shaped be assembled into the finished product battery behind the ripe pole plate.Preferably, above-mentioned battery is plumbous carbon superbattery.
A kind of typical embodiment according to the present invention, the preparation method of above-mentioned negative plate may further comprise the steps: 1) cell active materials, capacitance material and the agent of conduction steric hindrance are mixed, add entry and sulfuric acid solution then, make the GND lead plaster; 2) the GND lead plaster is filled on grid,, be cured under preferred 60 ℃, 95% above relative humidity, obtain negative pole and give birth to plate at 50～80 ℃; 3) negative pole is given birth to the negative plate that plate carries out obtaining after the chemical synthesis technology battery.Wherein, the addition of sulfuric acid is the 2-5% of active material total amount, and generally adopting density is 1.1～1.400g/cm
3Aqueous sulfuric acid.
To combine specific embodiment to further specify beneficial effect of the present invention below.
EXAMPLE l
Each constituent content of present embodiment negative pole is seen table 1; After cell active materials component, capacitance material component, conduction steric hindrance agent component mixed; Add entry, sulfuric acid respectively and in paste mixing machine, stir and make lead plaster, will fill on grid, under 60 degree, 98% relative humidity, be cured with the lead plaster that makes; Obtain green plate after the 70 degree dryings, obtain the negative ripe pole plate of battery after green plate is changed into.
Positive plate in the present embodiment adopts traditional lead-acid battery positive plate manufacture method to make, will just ripe pole plate and battery bear ripe pole plate and be assembled into battery and carry out performance test.
In the present embodiment, after the active carbon of high-load added, negative pole had good capacitance characteristic; When under 50% part charging state, carrying out high current charge-discharge, the active carbon electric double layer capacitance is born the part electric current, suppresses the formation of fine and close sulfuric acid lead layer; Make negative pole have longer cycle life; And the inferior titanium oxide of trace adds in the cathode lead plaster, has regulated the porosity and the aperture of negative pole, suppresses lead sulfate crystal growing up in air strike in the deep discharge cyclic process; The inferior titanium oxide of Magneli phase has the conductivity close with graphite, has therefore improved the charge acceptance and the low temperature discharge ability of plumbous negative pole.
Result of the test shows: its dark cycle life reaches 440 times; Be higher than 410 times of traditional lead acid batteries; Part charging state cycle-index reaches 77000 times; Be higher than 4721 times of conventional batteries far away, compare the cold-starting ability with traditional lead acid batteries and improved 15%, charge acceptance has improved 3.7%.
Embodiment 2
Each constituent content of present embodiment negative pole is seen table 1; After cell active materials component, capacitance material component, conduction steric hindrance agent component mixed; Add entry, sulfuric acid respectively and in paste mixing machine, stir and make lead plaster, will fill on grid, under 60 degree, 98% relative humidity, be cured with the lead plaster that makes; Obtain green plate after the 70 degree dryings, obtain the negative ripe pole plate of battery after green plate is changed into.Positive plate in the present embodiment adopts traditional lead-acid battery positive plate manufacture method to make, will just ripe pole plate and battery bear ripe pole plate and be assembled into battery and carry out performance test.
In the present embodiment, the interpolation of active carbon makes negative pole have good capacitance characteristic, when under 50% part charging state, carrying out high current charge-discharge; The active carbon electric double layer capacitance is born the part electric current; Suppress the formation of fine and close sulfuric acid lead layer, make negative pole have longer cycle life, inferior titanium oxide adds in the cathode lead plaster; The porosity and the aperture of negative pole have been regulated; Suppress lead sulfate crystal growing up in air strike in the deep discharge cyclic process, the inferior titanium oxide of Magneli phase has the conductivity close with graphite, has therefore improved the charge acceptance and the low temperature discharge ability of plumbous negative pole.
Result of the test shows: its dark cycle life reaches 1152 times, is higher than traditional lead acid batteries, and part charging state cycle-index reaches 80000 times, is higher than 20 times of conventional batteries, and the cold-starting ability has improved 62%, and charge acceptance has improved 11.3%.
Embodiment 3
Each constituent content of present embodiment negative pole is seen table 1; After cell active materials component, capacitance material component, conduction steric hindrance agent component mixed; Add entry, sulfuric acid respectively and in paste mixing machine, stir and make lead plaster, will fill on grid, under 60 degree, 98% relative humidity, be cured with the lead plaster that makes; Obtain green plate after the 70 degree dryings, obtain the negative ripe pole plate of battery after green plate is changed into.Positive plate in the present embodiment adopts traditional lead-acid battery positive plate manufacture method to make, will just ripe pole plate and battery bear ripe pole plate and be assembled into battery and carry out performance test.
In the present embodiment, the interpolation of active carbon makes negative pole have good capacitance characteristic, when under 50% part charging state, carrying out high current charge-discharge; The active carbon electric double layer capacitance is born the part electric current; Suppress the formation of fine and close sulfuric acid lead layer, make negative pole have longer cycle life, inferior titanium oxide adds in the cathode lead plaster; The porosity and the aperture of negative pole have been regulated; Suppress lead sulfate crystal growing up in air strike in the deep discharge cyclic process, the inferior titanium oxide of Magneli phase has the conductivity close with graphite, has therefore improved the charge acceptance and the low temperature discharge ability of plumbous negative pole.
Result of the test shows: its dark cycle life reaches 800 times, is higher than traditional lead acid batteries, and part charging state cycle-index reaches 6000 times, is higher than conventional batteries, and the cold-starting ability has improved 55.4%, and charge acceptance has improved 6.2%.
Embodiment 4
In the present embodiment, the interpolation of active carbon makes negative pole have good capacitance characteristic, when under 50% part charging state, carrying out high current charge-discharge; The active carbon electric double layer capacitance is born the part electric current; Suppress the formation of fine and close sulfuric acid lead layer, make negative pole have longer cycle life, inferior titanium oxide adds in the cathode lead plaster; The porosity and the aperture of negative pole have been regulated; Suppress lead sulfate crystal growing up in air strike in the deep discharge cyclic process, the inferior titanium oxide of Magneli phase has the conductivity close with graphite, has therefore improved the charge acceptance and the low temperature discharge ability of plumbous negative pole.
Each constituent content of present embodiment negative pole is seen table 1; After cell active materials component, capacitance material component, conduction steric hindrance agent component mixed; Add entry, sulfuric acid respectively and in paste mixing machine, stir and make lead plaster, will fill on grid, under 60 degree, 98% relative humidity, be cured with the lead plaster that makes; Obtain green plate after the 70 degree dryings, obtain the negative ripe pole plate of battery after green plate is changed into.Positive plate in the present embodiment adopts traditional lead-acid battery positive plate manufacture method to make, will just ripe pole plate and battery bear ripe pole plate and be assembled into battery and carry out performance test.
Result of the test shows: its dark cycle life reaches 1031 times, is higher than traditional lead acid batteries, and part charging state cycle-index reaches 78000 times, is higher than conventional batteries, and the cold-starting ability has improved 59.3%, and charge acceptance has improved 9.1%.
Embodiment 5
Each constituent content of present embodiment negative pole is seen table 1; After cell active materials component, capacitance material component, conduction steric hindrance agent component mixed; Add entry, sulfuric acid respectively and in paste mixing machine, stir and make lead plaster, will fill on grid, under 60 degree, 98% relative humidity, be cured with the lead plaster that makes; Obtain green plate after the 70 degree dryings, obtain the negative ripe pole plate of battery after green plate is changed into.Positive plate in the present embodiment adopts traditional lead-acid battery positive plate manufacture method to make, will just ripe pole plate and battery bear ripe pole plate and be assembled into battery and carry out performance test.
In the present embodiment; The interpolation of active carbon makes negative pole have good capacitance characteristic, and when under 50% part charging state, carrying out high current charge-discharge, the active carbon electric double layer capacitance is born the part electric current; Suppress the formation of fine and close sulfuric acid lead layer; Make negative pole have longer cycle life, the inferior titanium oxide that replaces the Magneli phase with the plumbic acid barium of high conductivity adds in the cathode lead plaster, can regulate the porosity and the aperture of negative pole equally; Suppress lead sulfate crystal growing up in air strike in the deep discharge cyclic process, improve the charge acceptance and the low temperature discharge ability of plumbous negative pole.
Result of the test shows: its dark cycle life reaches 970 times, is higher than traditional lead acid batteries, and part charging state cycle-index reaches 77200 times, is higher than conventional batteries, and the cold-starting ability has improved 47%, and charge acceptance has improved 8.3%.
Embodiment 6
Each constituent content of present embodiment negative pole is seen table 1; After cell active materials component, capacitance material component, conduction steric hindrance agent component mixed; Add entry, sulfuric acid respectively and in paste mixing machine, stir and make lead plaster, will fill on grid, under 60 degree, 98% relative humidity, be cured with the lead plaster that makes; Obtain green plate after the 70 degree dryings, obtain the negative ripe pole plate of battery after green plate is changed into.Positive plate in the present embodiment adopts traditional lead-acid battery positive plate manufacture method to make, will just ripe pole plate and battery bear ripe pole plate and be assembled into battery and carry out performance test.
In the present embodiment; The interpolation of active carbon makes negative pole have good capacitance characteristic, and when under 50% part charging state, carrying out high current charge-discharge, the active carbon electric double layer capacitance is born the part electric current; Suppress the formation of fine and close sulfuric acid lead layer; Make negative pole have longer cycle life, the mutually inferior titanium oxide of Magneli that mixes is added in the cathode lead plaster, can regulate the porosity and the aperture of negative pole equally; Suppress lead sulfate crystal growing up in air strike in the deep discharge cyclic process, improve the charge acceptance and the low temperature discharge ability of plumbous negative pole.
Result of the test shows: its dark cycle life reaches 698 times, is higher than traditional lead acid batteries, and part charging state cycle-index reaches 78500 times, is higher than conventional batteries, and the cold-starting ability has improved 31%, and charge acceptance has improved 4.8%.
Embodiment 7
Each constituent content of present embodiment negative pole is seen table 1; After cell active materials component, capacitance material component, conduction steric hindrance agent component mixed; Add entry, sulfuric acid respectively and in paste mixing machine, stir and make lead plaster, will fill on grid, under 60 degree, 98% relative humidity, be cured with the lead plaster that makes; Obtain green plate after the 70 degree dryings, obtain the negative ripe pole plate of battery after green plate is changed into.Positive plate in the present embodiment adopts traditional lead-acid battery positive plate manufacture method to make, will just ripe pole plate and battery bear ripe pole plate and be assembled into battery and carry out performance test.
In the present embodiment, the interpolation of active carbon makes negative pole have good capacitance characteristic, when under 50% part charging state, carrying out high current charge-discharge; The active carbon electric double layer capacitance is born the part electric current; Suppress the formation of fine and close sulfuric acid lead layer, make negative pole have longer cycle life, inferior titanium oxide adds in the cathode lead plaster; The porosity and the aperture of negative pole have been regulated; Suppress lead sulfate crystal growing up in air strike in the deep discharge cyclic process, the inferior titanium oxide of Magneli phase has the conductivity close with graphite, has therefore improved the charge acceptance and the low temperature discharge ability of plumbous negative pole.
Result of the test shows: its dark cycle life reaches 1140 times, is higher than traditional lead acid batteries, and part charging state cycle-index reaches 79100 times, is higher than conventional batteries, and the cold-starting ability has improved 55%, and charge acceptance has improved 7.7%.
Embodiment 8
Each constituent content of present embodiment negative pole is seen table 1; After cell active materials component, capacitance material component mixed; Add entry, sulfuric acid respectively and in paste mixing machine, stir and make lead plaster, will fill on grid, under 60 degree, 98% relative humidity, be cured with the lead plaster that makes; Obtain green plate after the 70 degree dryings, obtain the negative ripe pole plate of battery after green plate is changed into.Positive plate in the present embodiment adopts traditional lead-acid battery positive plate manufacture method to make, will just ripe pole plate and battery bear ripe pole plate and be assembled into battery and carry out performance test.
In the present embodiment, the interpolation of active carbon makes negative pole have good capacitance characteristic, when under 50% part charging state, carrying out high current charge-discharge; The active carbon electric double layer capacitance is born the part electric current; Suppress the formation of fine and close sulfuric acid lead layer, make negative pole have longer cycle life, do not add the agent of conduction steric hindrance in the present embodiment; The dark cycle life of battery does not significantly improve, and only omits height a bit than conventional batteries.
Result of the test shows: its dark cycle life reaches 470 times, and a little more than traditional lead acid batteries, part charging state cycle-index reaches 19250 times, is higher than conventional batteries, and the cold-starting ability has improved 24%, and charge acceptance has improved 2%.
Comparative Examples 1
This Comparative Examples is the negative ripe pole plate of conventional batteries that market is bought; Its each component of prescription is seen the Comparative Examples 1 in the table 1; The just ripe pole plate of traditional lead-acid battery that positive plate in this contrast case adopts market to buy is assembled into traditional lead acid batteries with positive and negative ripe pole plate and carries out performance test.
Result of the test shows: its dark cycle life of conventional batteries is 410 times, and part charging state cycle-index is 4721 times.
Table 1
Can find out that from the foregoing description the dark cycle life of substrate of the present invention, part charging state cycle-index, cold-starting ability, charge acceptance are greatly improved.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the negative plate of a battery is made up of grid and the negative material of full-filling on said grid, it is characterized in that said negative material comprises cell active materials, capacitance material, and the agent of conduction steric hindrance,
Wherein, said cell active materials comprises the lead powder of 100 weight portions, the barium sulfate of 0.6～2.0 weight portion, and the short fiber of 0.1～0.5 weight portion;
Said capacitance material comprises the active carbon of 0.1～10 weight portion; And
The addition of said conduction steric hindrance agent is 0.1～5.0 weight portion, and the agent of said conduction steric hindrance comprises mutually inferior titanium oxide of Magneli and/or plumbic acid barium.
2. according to the described negative plate of claim l, it is characterized in that the doped chemical in the mutually inferior titanium oxide of said Magneli is selected from one or more elements in the group of being made up of Nb, Co, V.
3. negative plate according to claim 1 is characterized in that said capacitance material also comprises one or more in the group of being made up of graphite, carbon fiber, CNT.
4. negative plate according to claim 1; It is characterized in that; Said capacitance material also comprises the agent of inhibition liberation of hydrogen; The agent of said inhibition liberation of hydrogen is selected from one or more in the group of being made up of oxide, hydroxide or the sulfate of lead, zinc, silver, bismuth, and the addition of said inhibition liberation of hydrogen agent is 0.01～1.0 weight portion.
5. negative plate according to claim 1 is characterized in that said capacitance material also comprises bonding agent, and said bonding agent is selected from one or more in the group of being made up of CMC, PTFE, PVDF, SBR, and the addition of said bonding agent is 0～1.0 weight portion.
6. negative plate according to claim 1 is characterized in that, said cell active materials also comprises and is selected from the group of being made up of lignin, humic acid, acetylene black one or more.
7. negative plate according to claim 1 is characterized in that, said negative material comprises the raw material of following weight portion:
Lead powder 100 weight portions,
Barium sulfate 1.2 weight portions,
Short fiber 0.2 weight portion,
Lignin 0.3 weight portion,
Humic acid 0.15 weight portion,
Active carbon 2 weight portions,
Acetylene black 0.2 weight portion, and
Mutually inferior titanium oxide 3 weight portions of Magneli.
8. a battery is characterized in that, said battery comprises like each described negative plate in the claim 1 to 7.
9. battery according to claim 8 is characterized in that, said battery is plumbous carbon superbattery.
10. the preparation method according to each described negative plate of claim 1-7 is characterized in that, may further comprise the steps:
1) said cell active materials, said capacitance material and the agent of said conduction steric hindrance are mixed, add entry and sulfuric acid solution then, make the GND lead plaster;
2) said GND lead plaster is filled on grid, under 50～80 ℃, 95% above relative humidity, be cured, obtain negative pole and give birth to plate;
3) said negative pole is given birth to the negative plate that plate carries out obtaining after the chemical synthesis technology said battery.
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| CN106129357B (en) * | 2016-07-14 | 2019-02-12 | 安徽轰达电源有限公司 | Deep glue-type spy consolidates lead carbon battery lead plaster |
| CN106450325A (en) * | 2016-08-31 | 2017-02-22 | 浙江平湖华龙实业股份有限公司 | Modified nanometer silicon-based oxide composite lead-acid battery of electric baby carriage |
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Application publication date: 20120919 |