CN106876718A - Lead-acid accumulator collector - Google Patents

Lead-acid accumulator collector Download PDF

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Publication number
CN106876718A
CN106876718A CN201510918620.8A CN201510918620A CN106876718A CN 106876718 A CN106876718 A CN 106876718A CN 201510918620 A CN201510918620 A CN 201510918620A CN 106876718 A CN106876718 A CN 106876718A
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China
Prior art keywords
lead
alloy
titanium
acid accumulator
clad
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Chinese (zh)
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杨春晓
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Individual
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention discloses a kind of lead-acid accumulator collector, it includes matrix and the clad being coated on outside matrix, and the material of described matrix includes conductive capability more than one or more in metal or metal alloy, CNT, the Graphene of Titanium；The material of the clad includes nonmetallic titanium compound, SnO2、SnO2One or more in composite.The present invention constitutes lead-acid accumulator collector using composite, relative to existing pure lead or metal grid, have the advantages that material apparent density is small, conductive capability is strong, mechanical strength is big, corrosion-resistant, liberation of hydrogen and overpotential for oxygen evolution are high, can effectively lift the performance of the aspects such as lead-acid accumulator gravimetric specific energy, gravimetric specific power, cycle life, resist passivation, guarantor's liquid.

Description

Lead-acid accumulator collector
Technical field
The present invention relates to lead-acid accumulator field, more particularly to lead-acid accumulator collector.
Background technology
Lead-acid accumulator collector, such as lead acid accumulator plate grid, for being distributed to the electric current inside lead-acid accumulator, being collected, conveyed, while also the active material or lead plaster to lead-acid accumulator have the effect of mechanical support, fixation.At present, the collector of wide variety of lead-acid accumulator, is essentially all to be made by metal or pure lead.Metal or pure lead collector, have the advantages that easy processing, corrosion-resistant, resistance to high oxidation potential, gassing overpotential high are more compatible with lead-acid accumulator electro-chemical systems, but, mechanical strength, corrosion resistance, material proportion, even on electric conductivity, it is not ideal enough, the performance of lead-acid accumulator, such as specific energy, service life, heavy-current discharge are constrained, so as to significantly limit application level and development space of the lead-acid accumulator in the field such as power and energy storage.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of lead-acid accumulator collector, and it can effectively lift the performances such as lead-acid accumulator gravimetric specific energy, gravimetric specific power, cycle life.
In order to solve the above technical problems, lead-acid accumulator collector of the invention, including matrix and the clad that is coated on outside matrix, the material of described matrix includes conductive capability more than one or more in metal or metal alloy, CNT, the Graphene of Titanium；The material of the clad includes nonmetallic titanium compound, SnO2、SnO2One or more in composite.
Wherein：
The conductive capability is more than the metal or metal alloy of Titanium, including but not limited to：One or more in silver or silver alloy, copper or copper alloy, aluminum or aluminum alloy, magnesium or magnesium alloy, iron or ferroalloy, lead or metal, nickel or nickel alloy, tin or tin alloy, calcium or calcium alloy, zinc or kirsite, tungsten or tungsten alloy, vanadium or vanadium alloy, antimony or antimony alloy, barium or barium alloy.
The SnO2Composite is SnO2The doped or non-doped composite for mixing and being formed in elementide aspect, atomic scale or their mixing aspect with one or more in nonmetallic titanium compound, lead, lead compound, Graphene, CNT, metal or metal alloy, organic polymer, inorganic polymer, tin class additive, titanium class additive, anode additive, cathode additive agent, sulfuric acid.
The nonmetallic titanium compound, including but not limited to：The doped or non-doped symbiosis blend for mixing and being formed on elementide aspect, atomic scale or in their mixing aspect for one or more in one or more in titanyl compound, sulfide, nitride, boride, carbide, hydride, hydroxide, silicide, and above-mentioned nonmetallic titanium compound.Wherein, titanyl compound is included but is not limited to：TiO2、TiO、Ti2O3、Ti3O5、Ti4O7、Ti5O9In one or more；The sulfide of titanium is included but is not limited to：TiS、TiS2、Ti2S3、TiS3In one or more；The nitride of titanium is included but is not limited to： TiN、TiN2、Ti2N、Ti3N、Ti4N、Ti3N4、Ti3N5、Ti5N6In one or more；The boride of titanium is included but is not limited to：Ti2B、TiB、TiB2、Ti2B5In one or more；The carbide of titanium is included but is not limited to：One kind in TiC, non-stoichiometry titanium carbide and various；The hydride of titanium is included but is not limited to：TiH、TiH2, one or more therein；The hydroxide of titanium is included but is not limited to：Ti(OH)2、Ti(OH)3、H4TiO4、H3TiO3, one or more in many metatitanic acids；The silicide of titanium is included but is not limited to：One or more in TiSi, non-stoichiometry titanium silicide.Hybrid materials in the symbiosis blend are also included but is not limited to：One or more in lead, lead compound, tin, tin ash, Graphene, CNT, metal or metal alloy, organic polymer, inorganic polymer, tin class additive, titanium class additive, anode additive, cathode additive agent, tin ash, the sulfuric acid of doping.
In as the material for mixing, lead compound is included but is not limited to：Brown lead oxide, lead monoxide, lead orthoplumbate, plumbous plumbate, lead monoxide (Pb2O), one or more in lead sulfate；Metal or metal alloy is included but is not limited to：One or more in silver or silver alloy, copper or copper alloy, aluminum or aluminum alloy, magnesium or magnesium alloy, iron or ferroalloy, lead or metal, nickel or nickel alloy, tin or tin alloy, calcium or calcium alloy, zinc or kirsite, tungsten or tungsten alloy, vanadium or vanadium alloy, antimony or antimony alloy, barium or barium alloy, titanium or titanium alloy, lithium or lithium alloy, sodium or sodium alloy；The organic polymer is included but is not limited to：Polyethylene, polypropylene, polyester, ABS；The inorganic polymer is included but is not limited to：One or more in glass, mica, asbestos, black phosphorus, phosphorus pentoxide, antimony pentoxide；The tin class additive is included but is not limited to：SnO2、SnSO4, one or more in SnO；The titanium class additive is included but is not limited to：Titanium, TiO2、TiO、Ti2O3、Ti3O5、Ti4O7、Ti5O9In one or more；The anode additive is included but is not limited to：Conductive agent, pore forming agent, dispersant, foaming agent, anode plate grid preservative, resistance to blunt agent, anti-premature capacity loss agent, cycle life improver, self discharge inhibitor, anti-positive material(PAM) softening agents for defoliating, adhesive, specifically, including but not limited to：Carbon materials (carbon black, anisotropic graphite, black phosphorus, aquadag, acetylene black, graphite, polyacene, carbon fiber), Graphene, tin ash are coated with the composite of tin ash and (are such as coated with SnO2Electro-conductive glass small pieces), titanium, anion/cation foaming agent (such as lauryl sodium sulfate, phosphoric acid, boric acid, cobaltous sulfate, magnesium sulfate, four basic lead sulphates, sodium carboxymethylcellulose, chopped fiber (terylene, Dynel, polypropylene, acrylic fiber, polytetrafluoroethylene (PTFE), carbon), conductive polymer additive is (such as the polyacetylene for adulterating or do not adulterate, polyacetylene copolymer, polyphenylacetylene, polyphenylacetylene copolymer, polypyrrole, polythiophene, polyphenyl time Asia ethene, polyaniline, polyparaphenylene, the polyethylene of I2 doping/PEO graft copolymer, dopant includes but is not limited to iodine, CNT, in Graphene one or more), reducing agent (such as HAS), antimonial or antimony, bismuth compound or bismuth, lithium compound or lithium, calcium salt, aluminium salt, zeolite, hollow glass micro-ball, silicic acid, SiO2, one or more in sodium acid carbonate；The cathode additive agent is included but is not limited to：Conductive agent, pore forming agent, dispersant, foaming agent, swelling agent, liberation of hydrogen retardant, cryogenic property Improve agent, oxygen-inhibiting agent, sulfate resistance agent, self discharge inhibitor, adhesive, specifically, including but not limited to：Carbon black, Graphene, tin ash, titanium, sponge titanium, conducting polymer, humic acid, lignosulphonates, lignin, the derivative of tanning agent, roasting glue, barium sulfate, antioxidant (alpha-Naphthol, betanaphthol, alpha-nitroso-beta-naphthol, stearic acid, zinc stearate, rosin, 1,2 acid, glycerine, boric acid), vanillic aldehyde.
Can be used to be doped in SnO2Or the element of nonmetallic titanium compound is included but is not limited to：One or more in F, Sb, Sn, Ca, Bi, Co, Ca, Al, Mg, N, P, O, C.In the present invention, the material after doping with ((being doped material) x doped chemicals y) represent, wherein, subscript y be non-zero positive rational number, for the relative molar amounts for representing doped chemical be doped material.For example, being doped with 0.1 part of mole of TiO of Sb2, it is expressed as ((TiO2)0.9Sb0.1)。
Preferably, can also include more than one layer of intermediate layer between described matrix and clad, the material in the intermediate layer is one or more in all material for can act as matrix or coating layer material.
Composite or symbiosis blend in elementide aspect described above, refer to associated materials each with micro-scale more than atomic scale or elementide yardstick (including but not limited to：In Cell dimensions, elementide, sub- nanometer, nanometer, crystallite, sub-micron, micron, millimeter one or more) carried out on one-dimensional, two-dimentional, three dimensions it is homogeneous or it is inhomogenous mix to be formed mix section bar material.For mixing section bar material in elementide aspect, in the present invention, represented with the expression formula of " (material 1) x- (material 2) y- ...-(material n) z ", wherein, subscript x, y ..., z be any non-zero positive rational number (i.e. positive integer than 0 and fraction), for representing that this mixes the relative molar amounts of the every kind of material for participating in mixing in section bar material.For example：Relative molar amounts ratio is 2:5:9:1 TiO2、PbO2、TiB2And SnO2Four kinds of materials mix " elementide aspect the mixes type " material granule (TiO to be formed2)2-(PbO2)5-(TiB2)9-SnO2Represent.The promiscuous mode of elementide aspect includes but is not limited to lamination and mixes, i.e., the promiscuous mode of two or more material layers superposition alternating with each other, for example, TiO2、TiB2、SnO2It can be every two layers of TiO that a kind of lamination of three kinds of material formation mixes2Between have three layers of TiB2With two-layer SnO2, wherein three layers of TiB separated from one another2The two-layer SnO separated from one another that material is clipped jointly by it2Material is isolated.
Composite or symbiosis blend on atomic scale described above, refer to associated materials each with the micro-scale of atom and carried out on one-dimensional, two-dimentional, three dimensions it is homogeneous or it is inhomogenous mix to be formed mix section bar material.In the present invention, with " the 1st kind of atom in material 1xaThe 2nd kind of atom in-material 1xb- ... the n atom in-material 1xz- ... the n atom zz in-material n " statement formula mixes section bar material representing a certain specific atomic scale; wherein; subscript xa, xb of atom ..., xz ..., zz be any non-zero positive rational number, for representing that this mixes the relative number or molal quantity of the every kind of material atom for participating in mixing in section bar material.For example：Relative molar amounts ratio is 1:1:1:1:0.5 from titanium nitride and lead oxide, titanium boride, four kinds of atoms of material of tin oxide, it mixes " atomic scale the mixes type " material to be formed, with Ti-O-Pb-B-Sn0.5Represent.
During elementide aspect mixes section bar material and atomic scale mixes section bar material, the quality of each material or element accounts for the corresponding ratio for mixing section bar material gross mass and is not less than 1ppb.
Thickness >=the 0.062nm of the clad of collector of the invention.
The shape and structure of collector of the invention can be using conventional grid structure (including but not limited to：Vertical rib checkering grid, diagonal bar bar modified grid, radial pattern grid, half radial pattern grid, the radial pattern grid containing plastic frame, the stretch grid, diamond check or hole grid), expanded type grid plate structure, woven fibre structure, Bar strip type structure, one or more in foam grid structure, honeycomb type grid structure of combination.The generalized shape structure of collector of the present invention also fluid confluence, circuit connecting unit, lead-out terminal including lead-acid accumulator.
Lead-acid accumulator collector of the invention employs composite, relative to existing pure lead or metal grid, have the advantages that material apparent density is small, conductive capability is strong, mechanical strength is big, corrosion-resistant, liberation of hydrogen and overpotential for oxygen evolution are high, the performance of the aspects such as lead-acid accumulator gravimetric specific energy, gravimetric specific power, cycle life, resist passivation, guarantor's liquid can be effectively lifted, the fields such as plate electrode, winding battery electrode, bipolar cell electrode, tubular cells electrode, lithium ion, nickel-hydrogen battery are can be applied to.
Brief description of the drawings
Fig. 1 is 4 kinds of structural representations of composite collector of the invention.Wherein, a figures are plate armatures, and b figures are column type structures, and c figures are hauling type structures, and d figures are takeup type structures.
Fig. 2 is the schematic cross-section that " clad/matrix " flat composite collector is obtained after plate level cutting.
Fig. 3 is the schematic cross-section that " clad/matrix " column type composite collector is obtained after the axis of a cylinder cutting of column type electrode.
Fig. 4 is the schematic cross-section that " clad/individual layer intermediate layer/matrix " flat composite collector is obtained after plate level cutting.
Fig. 5 is the schematic cross-section that " clad/individual layer intermediate layer/matrix " column type composite collector is obtained after the axis of a cylinder cutting of column type electrode.
Fig. 6 is the schematic cross-section that " clad/bilayer intermediate layer/matrix " flat composite collector is obtained after plate level cutting.
Fig. 7 is the schematic cross-section that " clad/bilayer intermediate layer/matrix " column type composite collector is obtained after the axis of a cylinder cutting of column type electrode.
Fig. 8 is the TiB of embodiment 192-TiO2In clad, TiB2And TiO2In the schematic diagram of elementide aspect lamination promiscuous mode.
Fig. 9 is the TiB of embodiment 222-TiO2-SnO2In clad, TiB2、TiO2And SnO2In the schematic diagram of elementide aspect lamination promiscuous mode.
Figure 10 is 4 specific admixture schematic diagrams of elementide aspect.Wherein, a figures are represented in the environment of the atom, elementide or crystallite of material one, be scattered here and there atom, elementide or the crystallite of each other isolated material two, wherein, the elementide or crystallite of material two can be made up of single phase, element or compound, can also be mixed with material one by cluster or micro crystal material smaller in scale and constituted, can also be made up of with orderly or unordered state on more microcosmic yardstick other multiple materials；In the environment of the atom, elementide or crystallite environment of b figure expression materials one, atom, elementide or the crystallite of the material two of one-dimensional, two-dimentional upper communication with one another are there is；C figures are represented in the environment of atom, elementide or crystallite environment of material one, there is the atom of the material two of communication with one another, elementide or crystallite on one-dimensional, two-dimentional, three-dimensional；D figures are represented material one, material two, the atom of material three, are mixed with more than one promiscuous modes between elementide or crystallite.
Figure 11 is atomic scale promiscuous mode schematic diagram.Different geometries represents different atoms in figure.A figures be the atom from multiple material atomic scale in order, have rule, mix with having lattice；B figures be the atom from multiple material atomic scale it is unordered, random, amorphous mix.
Description of reference numerals is as follows in figure：
1：Clad
2：Matrix
3：Intermediate layer
Specific embodiment
It is have more specifically to understand to technology contents of the invention, feature and effect, in conjunction with the drawings and specific embodiments, to the present invention, details are as follows：
Embodiment 1
The collector of the present embodiment is TiO2/ Al composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 a and Fig. 2, are flat grid structure, wherein, anode plate grid thickness is 2mm, and negative electrode grid thickness is 1.3mm；Material is by Al matrixes and the clad TiO for being wrapped in Al matrixes2Constitute, wherein TiO2Thickness be 1nm.
The composite collector is applied to the both positive and negative polarity of lead-acid accumulator, compared to pure lead or metal grid, the specific power of applied lead-acid accumulator can be made to improve 20%~61%, gravimetric specific energy improves 23%~40%, and gassing rate reduces 30%~52%.
Embodiment 2
The collector of the present embodiment is ((TiO2-TiB2)99.9-Sb0.1)/Al composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 c and Fig. 2, are the stretch grid structure, and slab lattice thickness is 2mm, and material is by Al matrixes and the doped ((TiO for being wrapped in Al matrixes2-TiB2)99.9-Sb0.1) coating layer material composition.Wherein, ((TiO2-TiB2)99.9-Sb0.1) TiO that is mixed by the elementide aspect for being doped with the Sb of 0.1% molar ratio of coating layer material2-TiB2Hybrid materials are constituted, and its thickness is 600nm.
The composite collector is applied to the positive pole of lead-acid accumulator, compared to pure lead or metal grid, the gravimetric specific power of applied lead acid battery positive electrode can be made to improve 37%~82%, gravimetric specific energy improves 27%~63%, gassing rate reduces 20%~69%, and collector cycle life improves 42%~78%.
Embodiment 3
The collector of the present embodiment is ((Ti3N4-SnO2)99.9Sb0.1)/Al composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 d and Fig. 2, are takeup type porous structure, and wall panel thickness is 1mm, and each Circularhole diameter is 4mm, hole center spacing 6mm；Its material is by Al matrixes and the ((Ti for being wrapped in Al matrixes3N4-SnO2)99.9Sb0.1) clad composition, wherein, clad ((Ti3N4-SnO2)99.9Sb0.1) material is by Ti3N4-SnO2Formed after the Sb of doped 0.1% molar ratio of elementide aspect hybrid materials, thickness is 50 μm.
The composite collector is applied to the positive pole of spirally wound lead acid battery, compared to pure lead or metal grid, the gravimetric specific power of the positive pole of applied lead-acid accumulator can be made to improve 31%~79%, gravimetric specific energy improves 27%~56%, gassing rate reduces 17%~35%, and the cycle life of collector improves 45%~96%.
Embodiment 4
The collector of the present embodiment is TiB2/ Cu composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 b and Fig. 3, are column type structure, and the radial diameter of cylinder is 3mm；Its material is by Cu matrixes and the TiB for being wrapped in Cu matrixes2Clad is constituted, wherein, clad TiB2Thickness is 10 μm.
The composite collector is applied to the tubular type negative pole of lead-acid accumulator, compared to pure lead or metal grid, the tensile strength of applied lead-acid battery negative pole plate grid can be made to improve 33%~93%, the gravimetric specific power of negative pole improves 32%~75%, gravimetric specific energy improves 31%~53%, gassing rate reduces 20%~37%, and collector cycle life improves 44%~80%.
Embodiment 5
The collector of the present embodiment is TiB2-TiO2/ Ag composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 b and Fig. 3, are column type structure, and the radial diameter of cylinder is 2mm, and it is by Ag matrixes and the TiB for being wrapped in Ag matrixes2-TiO2Hybrid materials clad is constituted, wherein, TiB2-TiO2Hybrid materials clad is by TiO2And TiB2With 1:1 molar ratio mixes in respective elementide aspect and forms, and its thickness is 10 μm.
The composite collector is applied to the positive pole of tube type lead-acid accumulator, compared to pure lead or metal grid, the gravimetric specific power of the positive pole of applied lead-acid accumulator can be made to improve 33%~51%, gravimetric specific energy improves 17%~39%, gassing rate reduces 25%~44%, and the cycle life of collector improves 38%~74%.
Embodiment 6
The collector of the present embodiment is TiB2/ Ti/Cu composite collectors, the composite constitute as shown in figure 4, collector structure be the stretch grid structure, slab lattice thickness is 1mm；Its material by Cu matrixes, be wrapped in the clad TiB of Cu matrixes2And between Cu matrixes and TiB2Ti intermediate layers between clad are constituted, wherein, TiB2Thickness be 10nm, the thickness in Ti intermediate layers is 1nm.
The composite collector is applied to the both positive and negative polarity of lead-acid accumulator, compared to pure lead or metal grid, the tensile strength of the grid of applied lead-acid accumulator can be made to improve 35%~98%, the gravimetric specific power of battery improves 36%~89%, gravimetric specific energy improves 30%~51%, gassing rate reduces 25%~40%, and the cycle life of collector improves 35%~79%.
Embodiment 7
The collector of the present embodiment is Ti-B2- P/Ti/Pb composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 a and Fig. 4, are flat grid structure, and slab lattice thickness is 2mm；Its material by Pb matrixes, be wrapped in the Ti-B of Pb matrixes2- P hybrid materials clad and the Ti intermediate layers between Pb matrixes and clad are constituted.Wherein, clad Ti-B2- P hybrid materials are by TiB2With black P with 1:1 molar ratio mixes in atomic scale and forms, and its thickness is 100nm.The thickness in Ti intermediate layers is 10nm.
The composite collector is applied to the positive pole of spirally wound lead acid battery, compared to pure lead or metal grid, the gassing rate of applied lead-acid accumulator can be made to reduce 25%~65%, collector cycle life improves 34%~70%.
Embodiment 8
The collector of the present embodiment is Ti-B2-Pb-O2/ Pb/AlPb composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 a and Fig. 4, are flat grid structure, and thickness is 1mm, its material by AlPb alloy matrix aluminums, be wrapped in the Ti-B of AlPb alloy matrix aluminums2-Pb-O2Hybrid materials clad and the Pb individual layers intermediate layer between AlPb alloy matrix aluminums and clad are constituted.Wherein Ti-B2-Pb-O2Hybrid materials clad is by TiB2And PbO2With 1:1 molar ratio mixes in respective atomic scale and forms, and its thickness is 50nm.Pb intermediate layer thickness is 100nm.
The composite collector is applied to the positive pole of lead-acid accumulator, compared to pure lead or metal grid, the gravimetric specific power of applied lead acid battery positive electrode can be made to improve 38%~59%, gravimetric specific energy improves 24%~45%, gassing rate reduces by 23%~57%, collector cycle life extension 24%~52%.
Embodiment 9
The collector of the present embodiment is TiO2-PbO2/ TiPb/Al composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 a and Fig. 4, are flat grid shape structure, and thickness is 1mm.Its material by Al matrixes, be wrapped in the TiO of Al matrixes2-PbO2Hybrid materials clad and the TiPb titanium alloy individual layers intermediate layer between Al matrixes and clad are constituted.Wherein, TiO2-PbO2Hybrid materials clad is by TiO2And PbO2With 1:1 molar ratio mixes in respective elementide aspect and forms, and its thickness is 10 μm.TiPb intermediate layer thickness is 1 μm.
The composite collector is applied to the positive pole of lead-acid accumulator, compared to pure lead or metal grid, the gravimetric specific power of applied lead acid battery positive electrode can be made to improve 25%~73%, gravimetric specific energy improves 24%~49%, gassing rate reduces by 25%~54%, collector cycle life extension 44%~85%.
Embodiment 10
The collector of the present embodiment is Ti-O4- Pb/TiB/Al composite collectors, the composite is constituted as shown in figure 4, the structure of collector is takeup type porous structure, and wall panel thickness is 1mm, and each Circularhole diameter is 4mm, hole center spacing 6mm.Its material by Al matrixes, be wrapped in the Ti-O of Al matrixes4- Pb clads and between Al matrixes and Ti-O4TiB intermediate layers between-Pb clads are constituted.Wherein, Ti-O4- Pb clads are by TiO2And PbO2With 1:1 molar ratio mixes in atomic scale and forms, and its thickness is 100nm.The thickness in TiB intermediate layers is 20nm.
The composite collector is applied to the positive pole of spirally wound lead acid battery, compared to pure lead or metal grid, the gravimetric specific power of the positive pole of applied lead-acid accumulator can be made to improve 33%~45%, gravimetric specific energy improves 21%~44%, and gassing rate reduces 22%~65%.
Embodiment 11
The collector of the present embodiment is TiB2- acetylene black/TiC/CuTiSn composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 b and Fig. 5, are column type structure, and the radial diameter of cylinder is 3mm.Its material by CuTiSn copper alloy matrix, be wrapped in the TiB of CuTiSn copper alloy matrix2- acetylene black hybrid materials clad and the TiC intermediate layers between matrix and clad are constituted.Wherein, clad TiB2- acetylene black hybrid materials are by TiB2With acetylene black with 1:1 molar ratio mixes in elementide aspect and forms, and its thickness is 200nm.The thickness in TiC intermediate layers is 30nm.
The composite collector is applied to the tubular type negative pole of lead-acid accumulator, compared to pure lead or metal grid, the tensile strength of applied lead-acid battery negative pole plate grid can be made to improve 30%~92%, the gravimetric specific power of negative pole improves 30%~65%, gravimetric specific energy improves 25%~41%, and gassing rate reduces 24%~50%.
Embodiment 12
The collector of the present embodiment is Ti-O-B/Ti/Al composite collectors, and the structure and composite of the collector are constituted as shown in Fig. 1 b and Fig. 5, is column type structure, and the radial diameter of cylinder is 3mm.Its material by Al matrixes, be wrapped in the Ti-O-B hybrid materials clad of Al matrixes and the Ti individual layers intermediate layer between Al matrixes and Ti-O-B clads is constituted.Wherein, Ti-O-B hybrid materials clad is by TiO2And TiB2With 1:1 molar ratio mixes in atomic scale and forms, and its thickness is 1000nm.The thickness in Ti intermediate layers is 100nm.
The composite collector is applied to the positive pole of tube type lead-acid accumulator, compared to pure lead or metal grid, the gravimetric specific power of the positive pole of applied lead-acid accumulator can be made to improve 21%~45%, gravimetric specific energy improves 15%~32%, gassing rate reduces 23%~43%, and the cycle life of collector improves 25%~60%.
Embodiment 13
The collector of the present embodiment is TiC- activated carbons/TiC/Pb composite collectors, and the structure and composite of the collector are constituted as shown in Fig. 1 a and Fig. 4, are flat grid structure, and thickness is 2mm.Its material by Pb matrixes, be wrapped in the TiC- activated carbon hybrid materials clads of Pb matrixes and the TiC individual layers intermediate layer between Pb matrixes and TiC- active charcoal bag coating is constituted.Wherein, TiC- activated carbons hybrid materials clad presses 1 by TiC and activated carbon:1 molar ratio mixes in elementide aspect and forms, and its thickness is 400nm.TiC intermediate layer thickness is 100nm.
The composite collector is applied to the negative pole of lead-acid accumulator, the gravimetric specific power of the negative electrode grid of applied lead-acid accumulator can be made to improve 32%~65%, gravimetric specific energy improves 27%~55%, and gassing rate reduces 18%~41%.
Embodiment 14
The collector of the present embodiment is ((SnO2)99.7-P0.3)/Ti(OH)2/ Cu composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 b and Fig. 5, are cylindrical-shaped structure, and the radial diameter of cylinder is 3mm, its material by Cu matrixes, be wrapped in the ((SnO of Cu matrixes2)99.7-P0.3) material clad and between Cu matrixes and ((SnO2)99.7-P0.3) Ti (OH) between clad2Individual layer intermediate layer is constituted.Wherein, ((SnO2)99.7-P0.3) clad is by being doped with the SnO of the P of 0.3% molar ratio2Constitute, its thickness is 300nm.Ti(OH)2Intermediate layer thickness is 10nm.
The composite collector is applied to the positive pole of tube type lead-acid accumulator, compared to pure lead or metal grid, the tensile strength of the grid of applied lead-acid accumulator can be made to improve 23%~79%, the gravimetric specific power of positive pole improves 44%~67%, gravimetric specific energy and improves 32%~59%, and gassing rate reduces 28%~42%.
Embodiment 15
The collector of the present embodiment is ((TiO2)99.5-Sb0.5)/TiB2/ Al composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 b and Fig. 5, are column type structure, and the radial diameter of cylinder is 3mm, its material by Al matrixes, be wrapped in the ((TiO of Al matrixes2)99.5-Sb0.5) clad and between Al matrixes and ((TiO2)99.5-Sb0.5) TiB between clad2Intermediate layer is constituted.Wherein, ((TiO2)99.5-Sb0.5) clad is by being doped with the TiO of the Sb of 0.5% molar ratio2Constitute, its thickness is 30nm.TiB2Intermediate layer thickness is 100nm.
The composite collector is applied to the positive pole of tube type lead-acid accumulator, compared to pure lead or metal grid, the gravimetric specific power of applied lead acid battery positive electrode can be made to improve 33%~70%, gravimetric specific energy improves 29%~56%, and gassing rate reduces 29%~61%.
Embodiment 16
The collector of the present embodiment is TiO2/TiB2/ Ti/Al composite collectors, the composite of the fluid confluence constitute as shown in fig. 6, its material by Al matrixes, be wrapped in the TiO of Al matrixes2Clad and between Al matrixes and TiO2TiB between clad2, Ti two-layers intermediate layer constitute.Wherein, TiO2The thickness of clad is 20nm, TiB2The thickness in intermediate layer is 1 μm, and the thickness in Ti intermediate layers is 100nm.
The positive/negative plate that the composite fluid confluence is applied to lead-acid accumulator confluxes, and compared to pure lead or metal grid, the volume of applied lead-acid accumulator, gravimetric specific power can be made to improve 43%~90%, and fluid confluence cycle life improves 38%~79%.
Embodiment 17
The collector of the present embodiment is SnO2/PbO2/TiB2/ Ti/Al composite collectors, the structure and composite of the collector are constituted as illustrated in figure 1 c, are hauling type structure, and thickness is 1mm, its material by Al matrixes, be wrapped in the SnO of Al matrixes2Clad and the PbO between Al matrixes and clad2、TiB2, tri- layers of intermediate layers of Ti constitute.Wherein, SnO2Coating thickness is 100 μm, PbO2The thickness in intermediate layer is 200nm, TiB2The thickness in intermediate layer is 700nm, and the thickness in Ti intermediate layers is 100nm.
The composite collector is applied to the positive pole of spirally wound lead acid battery, compared to pure lead or metal grid, the gravimetric specific power of the positive pole of applied lead-acid accumulator can be made to improve 11%~37%, gravimetric specific energy improves 8%~20%, and gassing rate reduces 30%~51%.
Embodiment 18
The collector of the present embodiment is TiH2/ TiN/Ti/Ag composite collectors, the structure and composite of the collector are constituted as shown in Fig. 1 b and Fig. 7, are column type structure, and the radial diameter of cylinder is 3mm.Its material by Ag matrixes, be wrapped in the TiH of Ag matrixes2Clad and between Ag matrixes and TiH2TiN, Ti two-layer intermediate layer between clad is constituted.Wherein, TiH2The thickness of clad is 100nm, and the thickness in TiN intermediate layers and Ti intermediate layers is respectively 5nm.
The composite collector is applied to the negative pole of lead-acid accumulator, compared to pure lead or metal grid, the tensile strength of the negative electrode grid of applied lead-acid accumulator can be made to improve 22%~74%, the gravimetric specific power of GND improves 25%~54%, gravimetric specific energy improves 16%~35%, gassing rate reduces 43%~73%, and the cycle life of collector improves 32%~90%.
Embodiment 19
The collector of the present embodiment is TiB2-TiO2/ Ti/Al composite collectors, the structure of the collector is flat grid structure as shown in Figure 1a, and slab lattice thickness is 2mm.Its material by Al matrixes, be wrapped in the TiB of Al matrixes2-TiO2Laminated type hybrid materials clad and between Al matrixes and TiB2-TiO2Ti intermediate layers between clad are constituted.Wherein, TiB2-TiO2Laminated type hybrid materials clad is by TiB2And TiO2Elementide aspect is alternating with each other to fold to fall to mixing and forms, as shown in figure 8, every layer of TiB2And TiO2Thickness can be the same or different.In the present embodiment, the gross thickness of clad is 1200nm, every layer of TiB2Thickness be 100nm, every layer of TiO2Thickness be 20nm.The thickness in Ti intermediate layers is 100nm.
The composite collector is applied to the positive pole of flat lead-acid accumulator, compared to pure lead or metal grid, the gravimetric specific power of the anode plate grid of applied lead-acid accumulator can be made to improve 35%~77%, gravimetric specific energy improves 34%~58%, gassing rate reduces 23%~39%, and collector cycle life improves 43%~81%.
Embodiment 20
The collector of the present embodiment is Ti-B2-Sn-O2/ Ti-Sn-B/Cu composite collectors, the structure of the collector is flat grid grid structure as shown in Figure 1a.Its material by Cu matrixes, be wrapped in the Ti-B of Cu matrixes2-Sn-O2Hybrid materials clad and between Cu matrixes and Ti-B2-Sn-O2Ti-Sn-B hybrid materials intermediate layer between clad is constituted.Wherein, Ti-B2-Sn-O2Clad is by SnO2And TiB2With 1:1 molar ratio mixes in atomic scale and forms, and its thickness is 0.1nm；Ti-Sn-B intermediate layers are by TiB and Sn with 1:1 molar ratio mixes in atomic scale and forms, and its thickness is 10nm.
The composite collector is applied to the positive pole of flat lead-acid accumulator, compared to pure lead or metal grid, the tensile strength of applied lead acid battery positive electrode can be made to improve 22%~84%, gravimetric specific power improves 30%~63%, gravimetric specific energy improves 22%~57%, and gassing rate reduces 39%~80%.
Embodiment 21
The collector of the present embodiment is TiB2-SnO2/ TiCu/Cu composite collectors, the structure of the collector is foam grid, its material by Cu matrixes, be wrapped in the TiB of Cu matrixes2-SnO2Hybrid materials clad and between Cu matrixes and TiB2-SnO2TiCu alloy interlayers between clad are constituted.Wherein, TiB2-SnO2Clad is by SnO2And TiB2With 1:1 molar ratio mixes in elementide aspect and forms, and its thickness is 500 μm；TiCu alloy interlayers thickness is 10 μm.
The composite collector is applied to the positive pole of lead-acid accumulator, compared to pure lead or metal grid, the gravimetric specific power of applied lead acid battery positive electrode can be made to improve 26%~42%, gravimetric specific energy improves 12%~34%, gassing rate reduces 21%~32%, and collector cycle life improves 41%~87%.
Embodiment 22
The collector of the present embodiment is TiB2-TiO2-SnO2/ TiAl/Al composite collectors, the physical form structure of the collector is flat board, and thickness is 2mm.Its material by Al matrixes, be wrapped in the TiB of Al matrixes2-TiO2-SnO2Laminated type hybrid materials clad and between Al matrixes and TiB2-TiO2-SnO2TiAl alloy intermediate layer between clad is constituted.Wherein, TiB2-TiO2-SnO2Laminated type hybrid materials clad is by TiB2、TiO2And SnO2Elementide aspect it is alternating with each other fold to fall to mixing form, as shown in figure 9, the gross thickness of clad be 1020nm, every layer of TiB2Thickness be 100nm, every layer of TiO2Thickness be 10nm, every layer of SnO2Thickness be 15nm.The thickness in TiAl intermediate layers is 100nm.
The composite collector is applied to bipolar lead acid battery, compared to pure lead or metal grid, the gravimetric specific power of the grid of applied bipolar lead acid battery can be made to improve 21%~55%, gravimetric specific energy improves 5%~60%, gassing rate reduces 24%~41%, and collector cycle life improves 42%~83%.

Claims (14)

1. lead-acid accumulator collector, it is characterised in that including matrix and the clad being coated on outside matrix, the material of described matrix Material includes conductive capability more than one or more in metal or metal alloy, CNT, the Graphene of Titanium；The bag The material of coating includes nonmetallic titanium compound, SnO2、SnO2One or more in composite.
2. lead-acid accumulator collector according to claim 1, it is characterised in that the conductive capability is more than Titanium Metal or metal alloy, including：Silver-colored or silver alloy, copper or copper alloy, aluminum or aluminum alloy, magnesium or magnesium alloy, iron or ferroalloy, Lead or metal, nickel or nickel alloy, tin or tin alloy, calcium or calcium alloy, zinc or kirsite, tungsten or tungsten alloy, vanadium or vanadium are closed One or more in gold, antimony or antimony alloy, barium or barium alloy.
3. lead-acid accumulator collector according to claim 1, it is characterised in that the SnO2Composite is SnO2 With nonmetallic titanium compound, lead, lead compound, Graphene, CNT, metal or metal alloy, organic polymer, nothing One or more in machine polymer, tin class additive, titanium class additive, anode additive, cathode additive agent, sulfuric acid is in original The doped or non-doped composite for mixing and being formed in sub- cluster aspect, atomic scale or their mixing aspect.
4. the lead-acid accumulator collector according to claim 1 or 3, it is characterised in that the nonmetallic titanium compound bag Include：One kind in titanyl compound, sulfide, nitride, boride, carbide, hydride, hydroxide, silicide Or it is various, and one or more in above-mentioned nonmetallic titanium compound is on elementide aspect, atomic scale or they mixed The doped or non-doped symbiosis blend for mixing and being formed in conjunction aspect.
5. lead-acid accumulator collector according to claim 4, it is characterised in that titanyl compound includes：TiO2、TiO、 Ti2O3、Ti3O5、Ti4O7、Ti5O9In one or more；The sulfide of titanium includes：TiS、TiS2、Ti2S3、TiS3In one Plant or various；The nitride of titanium includes：TiN、TiN2、Ti2N、Ti3N、Ti4N、Ti3N4、Ti3N5、Ti5N6In one kind or many Kind；The boride of titanium includes：Ti2B、TiB、TiB2、Ti2B5In one or more；The carbide of titanium includes：TiC, non-ization It is a kind of and various in stoichiometric silicon carbide titanium；The hydride of titanium includes：TiH、TiH2, one or more therein；The hydrogen-oxygen of titanium Compound includes：Ti(OH)2、Ti(OH)3、H4TiO4、H3TiO3, one or more in many metatitanic acids；The silicide of titanium includes：TiSi、 One or more in non-stoichiometry titanium silicide.
6. lead-acid accumulator collector according to claim 4, it is characterised in that mix material in the symbiosis blend Material also includes：Lead, lead compound, tin, tin ash, Graphene, CNT, metal or metal alloy, organic polymer Thing, inorganic polymer, tin class additive, titanium class additive, anode additive, cathode additive agent, doping tin ash, One or more in sulfuric acid.
7. the lead-acid accumulator collector according to claim 3 or 6, it is characterised in that as in the material for mixing, lead Compound includes：Brown lead oxide, lead monoxide, lead orthoplumbate, plumbous plumbate, Pb2One kind or many in O, lead sulfate Kind；Metal or metal alloy include silver or silver alloy, copper or copper alloy, aluminum or aluminum alloy, magnesium or magnesium alloy, iron or ferroalloy, Lead or metal, nickel or nickel alloy, tin or tin alloy, calcium or calcium alloy, zinc or kirsite, tungsten or tungsten alloy, vanadium or vanadium are closed One or more in gold, antimony or antimony alloy, barium or barium alloy, titanium or titanium alloy, lithium or lithium alloy, sodium or sodium alloy；Institute Stating organic polymer includes：Polyethylene, polypropylene, polyester, ABS；The inorganic polymer includes：Glass, mica, asbestos, One or more in black phosphorus, phosphorus pentoxide, antimony pentoxide；The tin class additive includes：SnO2、SnSO4、SnO In one or more；The titanium class additive includes：Titanium, TiO2、TiO、Ti2O3、Ti3O5、Ti4O7、Ti5O9In one kind Or it is various；The anode additive includes：Conductive agent, pore forming agent, dispersant, foaming agent, anode plate grid preservative, resistance to blunt Agent, anti-premature capacity loss agent, cycle life improver, self discharge inhibitor, anti-positive material(PAM) softening agents for defoliating, Adhesive；The cathode additive agent includes：Conductive agent, pore forming agent, dispersant, foaming agent, swelling agent, liberation of hydrogen retardant, Cryogenic property Improve agent, oxygen-inhibiting agent, sulfate resistance agent, self discharge inhibitor, adhesive.
8. the lead-acid accumulator collector according to claim 3 or 6, it is characterised in that the SnO of doping2In doping unit Element includes one or more in F, Sb, Sn, Ca, Bi, Co, Ca, Al, Mg, N, P, O, C.
9. lead-acid accumulator collector according to claim 3, it is characterised in that the promiscuous mode bag of elementide aspect Include the promiscuous mode of two or more material layers superposition alternating with each other.
10. the lead-acid accumulator collector according to claim 1-3,5-6,9 any one, it is characterised in that the base More than one layer of intermediate layer is also included between body and clad, the material in the intermediate layer is that can act as matrix or clad material One or more in all material of material.
11. lead-acid accumulator collectors according to claim 4, it is characterised in that between described matrix and clad also More than one layer of intermediate layer is included, during the material in the intermediate layer is all material for can act as matrix or coating layer material One or more.
12. lead-acid accumulator collectors according to claim 7, it is characterised in that between described matrix and clad also More than one layer of intermediate layer is included, during the material in the intermediate layer is all material for can act as matrix or coating layer material One or more.
13. lead-acid accumulator collectors according to claim 8, it is characterised in that between described matrix and clad also More than one layer of intermediate layer is included, during the material in the intermediate layer is all material for can act as matrix or coating layer material One or more.
14. lead-acid accumulator collectors according to claim 4, it is characterised in that in the nonmetallic titanium compound of doping Doped chemical include F, Sb, Sn, Ca, Bi, Co, Ca, Al, Mg, N, P, O, C in one or more.
CN201510918620.8A 2015-12-11 2015-12-11 Lead-acid accumulator collector Pending CN106876718A (en)

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN108023094A (en) * 2017-11-20 2018-05-11 双登集团股份有限公司 High power class lead acid accumulator plate grid blank surface processing method
CN108270013A (en) * 2017-12-28 2018-07-10 广州倬粤动力新能源有限公司 Alloy-coated material
CN108330568A (en) * 2017-12-28 2018-07-27 广州倬粤动力新能源有限公司 The preparation method of grid active nano carbon fiber
CN110571066A (en) * 2019-10-05 2019-12-13 浙江理工大学 Preparation method of aluminum sulfide cobalt-graphene oxide composite flexible carbon nanofiber
CN112397721A (en) * 2019-08-18 2021-02-23 杨春晓 Lead-acid storage battery composite current collector and battery
CN114229964A (en) * 2021-11-23 2022-03-25 东莞理工学院 With Ti4O7Preparation method and application of anode for surface etching and fluorination of substrate
CN115036515A (en) * 2022-08-12 2022-09-09 清华大学 Carbon nano material composite current collector, preparation method thereof, electrode and battery
CN116315144A (en) * 2022-11-10 2023-06-23 骆驼集团襄阳蓄电池有限公司 Low-voltage auxiliary battery for new energy vehicle
CN117855468A (en) * 2024-03-07 2024-04-09 河北奥冠电源有限责任公司 High-rate negative electrode active material of lead-acid battery, and preparation method and application thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108023094A (en) * 2017-11-20 2018-05-11 双登集团股份有限公司 High power class lead acid accumulator plate grid blank surface processing method
CN108270013A (en) * 2017-12-28 2018-07-10 广州倬粤动力新能源有限公司 Alloy-coated material
CN108330568A (en) * 2017-12-28 2018-07-27 广州倬粤动力新能源有限公司 The preparation method of grid active nano carbon fiber
CN112397721A (en) * 2019-08-18 2021-02-23 杨春晓 Lead-acid storage battery composite current collector and battery
CN110571066A (en) * 2019-10-05 2019-12-13 浙江理工大学 Preparation method of aluminum sulfide cobalt-graphene oxide composite flexible carbon nanofiber
CN114229964A (en) * 2021-11-23 2022-03-25 东莞理工学院 With Ti4O7Preparation method and application of anode for surface etching and fluorination of substrate
CN114229964B (en) * 2021-11-23 2023-04-11 东莞理工学院 With Ti 4 O 7 Preparation method and application of anode for surface etching and fluorination of substrate
CN115036515A (en) * 2022-08-12 2022-09-09 清华大学 Carbon nano material composite current collector, preparation method thereof, electrode and battery
CN116315144A (en) * 2022-11-10 2023-06-23 骆驼集团襄阳蓄电池有限公司 Low-voltage auxiliary battery for new energy vehicle
CN116315144B (en) * 2022-11-10 2023-09-26 骆驼集团襄阳蓄电池有限公司 Low-voltage auxiliary battery for new energy vehicle
CN117855468A (en) * 2024-03-07 2024-04-09 河北奥冠电源有限责任公司 High-rate negative electrode active material of lead-acid battery, and preparation method and application thereof
CN117855468B (en) * 2024-03-07 2024-05-14 河北奥冠电源有限责任公司 High-rate negative electrode active material of lead-acid battery, and preparation method and application thereof

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