CN104167551A - Preparation method of composite carbon material for lead-carbon super battery - Google Patents

Preparation method of composite carbon material for lead-carbon super battery Download PDF

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Publication number
CN104167551A
CN104167551A CN201410393777.9A CN201410393777A CN104167551A CN 104167551 A CN104167551 A CN 104167551A CN 201410393777 A CN201410393777 A CN 201410393777A CN 104167551 A CN104167551 A CN 104167551A
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CN
China
Prior art keywords
lead
acid battery
carbon material
preparation
carbon
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Pending
Application number
CN201410393777.9A
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Chinese (zh)
Inventor
杨飞
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BSB POWER Co Ltd (SHENZHEN)
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BSB POWER Co Ltd (SHENZHEN)
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Priority to CN201410393777.9A priority Critical patent/CN104167551A/en
Publication of CN104167551A publication Critical patent/CN104167551A/en
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Abstract

The invention discloses a preparation method of a composite carbon material for a lead acid battery. The preparation method is characterized by comprising the following steps: (1) adding a carbon material into a lead salt solution, uniformly stirring, then performing suction filtration, washing with water, and drying, so as to obtain a filter cake; (2) adding the filter cake obtained in the step (1) into a sulfuric acid solution, uniformly stirring, then performing suction filtration, washing with water until pH is 7, and drying, so as to obtain the composite carbon material for the lead acid battery; and (3) calculating the loading rate of the composite carbon material for the lead acid battery, if the loading rate of the composite carbon material for the lead acid battery is smaller than 80%, repeating the steps (1) and (2) until the loading rate of the composite carbon material for the lead acid battery is greater than or equal to 80%.By using the preparation method, the problems of non-uniformity in dispersion of the carbon material in a negative electrode of a lead-carbon super battery and small effective contact interface between the carbon material and an active substance are effectively solved. The composite carbon material can be directly used as the negative electrode of the lead acid battery or a negative electrode additive of the lead-carbon super battery, and the battery prepared from the composite carbon material has the characteristics of good charge acceptance, long high-current cycle life and long HRPSoC cycle life.

Description

The preparation method of carbon composite for a kind of plumbous charcoal superbattery
Technical field
The present invention relates to a kind of preparation method of Carbon Materials, be specifically related to the preparation method of lead-acid battery carbon composite, its carbon composite of preparing can, directly as the negative pole of lead-acid battery, also can be used as lead carbon battery cathode additive agent.
Background technology
Deficient year by year due to petroleum resources, greatly develop electric motor car particularly hybrid electric vehicle become the task of top priority.Lead-acid battery is that current technology is the most ripe, is most widely used, and the better energy storage device of fail safe, has therefore obtained paying close attention to widely.But due to the various shortcoming of lead-acid battery, make to work and be inhibited under its large multiplying power.And the appearance of Pb-C superbattery can be applied in hybrid electric vehicle lead-acid battery technology, become current ideal energy storage device.
Due to the development of electric motor car, need battery to there is large multiplying power, jumbo character, so large multiplying power energy storage Pb-C superbattery becomes the emphasis of current research.And at present there is a lot of deficiencies in Pb-C superbattery, first, because the operating potential interval of material with carbon element is lower than the operating potential interval of lead-acid battery, but will be by two kinds of electrode combinations, necessarily require its operating potential consistent.Secondly, because the operating voltage of lead-acid battery is in 2V left and right, this can make the liberation of hydrogen problem of material with carbon element become very serious, and separating out of hydrogen can produce serious influence to the performance of battery.In addition, for internal-mixing Pb-C superbattery, also require to there is good compatibility between material with carbon element and plumbous active material.
In the manufacture process of Pb-C superbattery, the addition manner of Carbon Materials is mainly to carry out mechanical mixture with lead powder at present.Because the density of lead powder is much larger than the density of Carbon Materials, both are difficult to make it to be uniformly distributed after mixing, and by the mode of mechanical mixture, effective contact interface of Carbon Materials and lead powder is less, can not give full play to the electricity of Carbon Materials and lead and capacitance characteristic.
Summary of the invention
Technical problem to be solved by this invention is to provide for the existing deficiency of addition manner of existing Carbon Materials the preparation method of a kind of lead-acid battery carbon composite, it adopts the method for adsorption and sedimentation at the coated lead sulfate particle in the surface of Carbon Materials, Carbon Materials can be dispersed in lead powder uniformly, and with the organic combination of active material, realize effective combination of the super electrical property of Carbon Materials and battery performance.
Technical problem to be solved by this invention can be achieved through the following technical solutions:
A preparation method for carbon composite for lead-acid battery, is characterized in that being made up of following steps:
(1), after Carbon Materials is added stirring in lead salt solution, suction filtration, washing, obtain filter cake after dry;
(2), after the filter cake of step (1) is joined stirring in sulfuric acid solution, suction filtration, to be washed to pH be 7, the dry lead-acid battery carbon composite that obtains;
(3) load factor of carbon composite for calculating lead-acid battery, if lead-acid battery is less than 80% by carbon composite load factor, repeats above step (1), (2), until carbon composite load factor >=80% for lead-acid battery.
In a preferred embodiment of the invention, described solubility lead salt is lead acetate, plumbi nitras, the one in lead citrate.
In a preferred embodiment of the invention, also regulate pH value to 6-8 after stirring in Carbon Materials is added to solubility lead salt.
In a preferred embodiment of the invention, described lead salt solution is the one in lead acetate solution, lead nitrate solution, lead citrate solution.
In a preferred embodiment of the invention, described Carbon Materials comprises one or more the mixture in active carbon, Graphene, acetylene black.
The present invention has effectively solved Carbon Materials and in plumbous charcoal superbattery negative pole, has disperseed inhomogeneous, few with the effective contact interface of active material problem.This carbon composite can directly be used as the negative pole of lead acid accumulator or the cathode additive agent as super lead carbon battery, and it is good that the battery of its making has charge acceptance, and the large current cycle life-span is long, the feature that HRPSoC has extended cycle life.
Brief description of the drawings
Fig. 1 is the SEM figure (amplifying 10,000 times) of existing Carbon Materials.
Fig. 2 is the SEM figure (amplifying 10,000 times) of lead-acid battery of the present invention carbon composite
Embodiment
Embodiment 1:
A preparation method for carbon composite for lead-acid battery, is made up of following steps:
(1), active carbon and acetylene black are stirred 5 hours for the ratio of 6:1 is mixed to join in the lead acetate solution of mass percent 40% in mass ratio, filter washing on a small quantity, the dry filter cake that obtains;
(2) above-mentioned filter cake being placed in to percentage by weight thick fog is that 50% sulfuric acid solution stirs 5 hours, filters, and being washed to PH is 7, the dry lead-acid battery carbon composite that obtains;
(3) load factor of carbon composite for calculating lead-acid battery, if lead-acid battery is less than 80% by carbon composite load factor, repeats above step (1), (2) until lead-acid battery carbon composite load factor >=80%.
Embodiment 2:
A preparation method for carbon composite for lead-acid battery, is made up of following steps:
(1), active carbon and acetylene black are stirred 5 hours for the ratio of 8:1 is mixed to join in the lead nitrate solution of mass percent 40% in mass ratio, filter washing on a small quantity, the dry filter cake that obtains;
(2) above-mentioned filter cake being placed in to percentage by weight thick fog is that 50% sulfuric acid solution stirs 5 hours, filters, and being washed to PH is 7, the dry lead-acid battery carbon composite that obtains;
(3) load factor of carbon composite for calculating lead-acid battery, if lead-acid battery is less than 80% by carbon composite load factor, repeats above step (1), (2) until lead-acid battery carbon composite load factor >=80%.
Embodiment 3:
A preparation method for carbon composite for lead-acid battery, is made up of following steps:
(1), active carbon and Graphene are stirred 5 hours for the ratio of 6:1 is mixed to join in the lead nitrate solution of mass percent 40% in mass ratio, filter washing on a small quantity, the dry filter cake that obtains;
(2) above-mentioned filter cake being placed in to percentage by weight thick fog is that 50% sulfuric acid solution stirs 5 hours, filters, and being washed to PH is 7, the dry lead-acid battery carbon composite that obtains;
(3) load factor of carbon composite for calculating lead-acid battery, if lead-acid battery is less than 80% by carbon composite load factor, repeats above step (1), (2) until lead-acid battery carbon composite load factor >=80%.
Embodiment 4:
A preparation method for carbon composite for lead-acid battery, is made up of following steps:
(1), active carbon and Graphene, acetylene black are stirred 5 hours for the ratio of 6:1:1 is mixed to join in the lead citrate solution of mass percent 40% in mass ratio, filter washing on a small quantity, the dry filter cake that obtains;
(2) above-mentioned filter cake being placed in to percentage by weight thick fog is that 50% sulfuric acid solution stirs 5 hours, filters, and being washed to PH is 7, the dry lead-acid battery carbon composite that obtains;
(3) load factor of carbon composite for calculating lead-acid battery, if lead-acid battery is less than 80% by carbon composite load factor, repeats above step (1), (2) until lead-acid battery carbon composite load factor >=80%.
Embodiment 5
The difference of the present embodiment and embodiment 1 is: in step (1), the pH value of solution is adjusted to 6 faintly acid with acetic acid, other step is identical with embodiment 1.
Embodiment 6
The difference of the present embodiment and embodiment 2 is: in step (1), the pH value of solution is adjusted to 6 faintly acid with acetic acid, other step is identical with embodiment 2.
Embodiment 7
The difference of the present embodiment and embodiment 3 is: in step (1), the pH value of solution is adjusted to 6 faintly acid with acetic acid, other step is identical with embodiment 3.
Embodiment 8
The difference of the present embodiment and embodiment 4 is: in step (1), the pH value of solution is adjusted to 6 faintly acid with acetic acid, other step is identical with embodiment 4.
Embodiment 9
The difference of the present embodiment and embodiment 1 is: in step (1), the pH value of solution is adjusted to 8 alkalescent with ammoniacal liquor or NaOH, other step is identical with embodiment 1.
Embodiment 10
The difference of the present embodiment and embodiment 2 is: in step (1), the pH value of solution is adjusted to 8 alkalescent with ammoniacal liquor or NaOH, other step is identical with embodiment 2.
Embodiment 11
The difference of the present embodiment and embodiment 3 is: in step (1), the pH value of solution is adjusted to 8 alkalescent with ammoniacal liquor or NaOH, other step is identical with embodiment 3.
Embodiment 12
The difference of the present embodiment and embodiment 4 is: in step (1), the pH value of solution is adjusted to 8 alkalescent with ammoniacal liquor or NaOH, other step is identical with embodiment 4.
Adopt lead-acid battery of the present invention carbon composite to be directly used as the negative pole of lead-acid battery, or as cathode additive agent, be assembled into after VRLA sealed cell, charge acceptance improves 1-2 doubly, HRPSoC cycle life improves 2-3 doubly, is a kind of desirable plumbous charcoal superbattery negative material and plumbous charcoal superbattery cathode additive agent.

Claims (5)

1. a preparation method for carbon composite for lead-acid battery, is characterized in that being made up of following steps:
(1), after Carbon Materials is added stirring in lead salt solution, suction filtration, washing, obtain filter cake after dry;
(2), after the filter cake of step (1) is joined stirring in sulfuric acid solution, suction filtration, to be washed to pH be 7, the dry lead-acid battery carbon composite that obtains;
(3) load factor of carbon composite for calculating lead-acid battery, if lead-acid battery is less than 80% by carbon composite load factor, repeats above step (1), (2), until carbon composite load factor >=80% for lead-acid battery.
2. preparation method as claimed in claim 1, is characterized in that, described solubility lead salt is lead acetate, plumbi nitras, the one in lead citrate.
3. preparation method as claimed in claim 1, is characterized in that, after stirring, also regulates pH value to 6-8 in Carbon Materials is added to solubility lead salt.
4. preparation method as claimed in claim 1, is characterized in that, described lead salt solution is the one in lead acetate solution, lead nitrate solution, lead citrate solution.
5. preparation method as claimed in claim 1, is characterized in that, described Carbon Materials comprises one or more the mixture in active carbon, Graphene, acetylene black.
CN201410393777.9A 2014-08-11 2014-08-11 Preparation method of composite carbon material for lead-carbon super battery Pending CN104167551A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104659350A (en) * 2015-02-26 2015-05-27 中南大学 Method for secondary modification of surface of active carbon material for super battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102723466A (en) * 2011-03-31 2012-10-10 湖南丰日电源电气股份有限公司 Super Pb-C battery negative plate
CN103035894A (en) * 2012-12-19 2013-04-10 浙江工业大学 Method for preparing composite modified material for lead carbon superbattery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102723466A (en) * 2011-03-31 2012-10-10 湖南丰日电源电气股份有限公司 Super Pb-C battery negative plate
CN103035894A (en) * 2012-12-19 2013-04-10 浙江工业大学 Method for preparing composite modified material for lead carbon superbattery

Non-Patent Citations (2)

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Title
GORAN D. VUKOVIC, ET AL.: "Removal of lead from water by amino modified multi-walled carbon nanotubes", 《CHEMICAL ENGINEERING JOURNAL》 *
郎笑石: "高倍率储能Pb-C超级电池负极的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104659350A (en) * 2015-02-26 2015-05-27 中南大学 Method for secondary modification of surface of active carbon material for super battery
CN104659350B (en) * 2015-02-26 2017-05-03 中南大学 Method for secondary modification of surface of active carbon material for super battery

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Application publication date: 20141126