CN114188531A - Battery cathode powder and preparation method and application thereof - Google Patents
Battery cathode powder and preparation method and application thereof Download PDFInfo
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- CN114188531A CN114188531A CN202111229416.7A CN202111229416A CN114188531A CN 114188531 A CN114188531 A CN 114188531A CN 202111229416 A CN202111229416 A CN 202111229416A CN 114188531 A CN114188531 A CN 114188531A
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- 239000000843 powder Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002699 waste material Substances 0.000 claims abstract description 89
- 239000002253 acid Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000007773 negative electrode material Substances 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000013543 active substance Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 31
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 20
- 230000004913 activation Effects 0.000 claims description 17
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 17
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 12
- 229910000464 lead oxide Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 2
- 230000000284 resting effect Effects 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 20
- 238000001994 activation Methods 0.000 abstract description 18
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 23
- 238000000926 separation method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste 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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/22—Forming of electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention relates to the field of recycling of waste lead-acid storage batteries, and discloses battery negative electrode powder, a preparation method and application thereof, wherein the method comprises the following steps: (1) connecting a waste positive plate with a positive electrode of a charger, connecting a waste negative plate with a negative electrode of the charger, and then electrifying and activating the waste positive plate and the waste negative plate in the presence of acid liquor to obtain an activated positive plate and an activated negative plate; (2) washing and drying the activated positive plate and the activated negative plate in sequence, and then separating grid paste to obtain a positive active material, a negative active material and a lead grid; (3) and roasting the positive electrode active substance and the negative electrode active substance together, and grinding a roasted product to obtain the battery negative electrode powder. By using a charging activation process in the preparation process, the content of PbO in the prepared negative electrode powder is higher than 99 wt%, and the cycle life of 100% DOD of a lead-acid storage battery prepared from the prepared negative electrode powder can reach more than 650 times.
Description
Technical Field
The invention relates to the field of recycling of waste lead-acid storage batteries, in particular to battery negative electrode powder, and a preparation method and application thereof
Background
The waste lead-acid storage battery mainly comprises components such as positive and negative lead pastes, a lead grid, lead pieces, a partition plate, electrolyte, a plastic shell and the like, wherein the waste lead paste is complex in composition and is difficult to recycle.
In the conventional recovery method, waste lead paste is desulfurized and then pyrometallurgically smelted to prepare refined lead, or the desulfurized product is prepared into lead oxide.
CN106252776B discloses a process for preparing battery negative electrode powder by using waste positive and negative electrode active materials, which comprises: respectively drying the scrapped positive plate and the scrapped negative plate, stripping a positive active material and a negative active material, then testing the contents of lead dioxide, lead oxide and lead sulfate in the positive active material and the negative active material, mixing and stirring the positive active material and dilute sulfuric acid, mixing the obtained reactive active material and the negative active material, adding sodium hydroxide for desulfurization, washing to be neutral after the reaction is finished, filtering to obtain lead paste and filtrate, and cooling, crystallizing and storing the filtrate; and carrying out vacuum drying on the lead plaster, and then carrying out ball milling to obtain the battery negative electrode powder with the oxidation degree of 70-80% and the average particle size of 2-3 mu m. The method has long preparation process, and needs acid solution and alkali solution successively, and the oxidation degree of the product is low.
The existing recycling method has the problems of long treatment process, high energy consumption, high consumption of chemical reagents and high cost. Therefore, the method for preparing the battery cathode powder by using the waste lead-acid storage battery is provided, and has important significance for reducing the production cost, simplifying the production flow and recycling wastes in a more environment-friendly manner.
Disclosure of Invention
The invention aims to solve the problems of long treatment process, high energy consumption, high consumption of chemical reagents and high cost of the method for recycling lead in the lead plaster of the waste lead-acid battery in the prior art and the problem that the recycled negative electrode powder is not ideal in the preparation of the lead-acid storage battery, and provides the battery negative electrode powder, the preparation method and the application.
To achieve the above object, a first aspect of the present invention provides a method for preparing a battery anode powder, comprising:
(1) connecting a waste positive plate with a positive electrode of a charger, connecting a waste negative plate with a negative electrode of the charger, and then electrifying and activating the waste positive plate and the waste negative plate in the presence of acid liquor to obtain an activated positive plate and an activated negative plate;
(2) washing and drying the activated positive plate and the activated negative plate in sequence, and then separating grid paste to obtain a positive active material, a negative active material and a lead grid;
(3) and roasting the positive electrode active substance and the negative electrode active substance together, and grinding a roasted product to obtain the battery negative electrode powder.
A second aspect of the invention provides a battery negative electrode powder produced by the method of the first aspect described above.
The third aspect of the invention provides the application of the negative electrode powder for the battery in the second aspect in the preparation of lead-acid storage batteries.
Through the technical scheme, the invention has the following beneficial effects:
(1) the waste positive plate and the waste negative plate are subjected to electrifying activation treatment, so that the lead sulfate in the waste positive plate and the waste negative plate can be converted into lead dioxide and free lead to a greater extent;
(2) the content of PbO in the prepared negative electrode powder is higher than 99 wt%, and when the negative electrode powder is used for preparing a lead-acid storage battery, the cycle life of 100% DOD can reach more than 650 times;
(3) the process flow is simple, the consumption of chemical reagents is low, and the cost is low.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic process flow diagram of the preparation of the battery negative electrode powder of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides, in a first aspect, a method for preparing a battery negative electrode powder, comprising:
(1) connecting a waste positive plate with a positive electrode of a charger, connecting a waste negative plate with a negative electrode of the charger, and then electrifying and activating the waste positive plate and the waste negative plate in the presence of acid liquor to obtain an activated positive plate and an activated negative plate;
(2) washing and drying the activated positive plate and the activated negative plate in sequence, and then separating grid paste to obtain a positive active material, a negative active material and a lead grid;
(3) and roasting the positive electrode active substance and the negative electrode active substance together, and grinding a roasted product to obtain the battery negative electrode powder.
According to the invention, in the step (1), the waste positive plates and the waste negative plates can be scrapped positive plates and negative plates obtained by crushing and separating the waste lead-acid storage battery. In the process of connecting the waste positive plate with the positive electrode of the charger and connecting the waste negative plate with the negative electrode of the charger, the collected waste positive plates can be firstly connected in parallel to form a waste positive electrode group, the collected waste negative plates can be connected in parallel to form a waste negative electrode group, and then the waste positive electrode group is connected with the positive electrode of the charger and the waste negative electrode group is connected with the negative electrode of the charger.
According to the invention, in the step (1), before the electrification activation, the waste positive plate and the waste negative plate connected with the charger in the previous step are preferably placed in the acid solution for standing. By standing in the acid solution, the acid solution can be uniformly diffused into the pores of the waste positive plate and the waste negative plate and further fully contacted with the positive active material and the negative active material. Preferably, the conditions of the standing may include: the temperature is 0-50 ℃ and the time is 0.5-1 h.
According to the invention, in the step (1), the acid solution can be a dilute sulfuric acid solution, and preferably a dilute sulfuric acid solution with the density of 1.05-1.10g/mL is adopted.
According to the present invention, in the step (1), the energization activation may be started after the end of the standing. Through the electrifying activation treatment, the lead sulfate in the waste polar plate can be converted into lead dioxide and free lead.
In the present invention, the process of energization activation may include: charging to voltage of 2.45-2.5V with 0.15C current, and charging for 5-10h with 0.05C current. More specifically, the waste positive plate and the waste negative plate are placed in a dilute sulfuric acid solution to be fully soaked and then charged with 0.15C current, the voltage quickly reaches 2.25-2.35V in the polarization state at the beginning, then the activation voltage starts to be stabilized at 2.2-2.3V for a long time when the outward diffusion speed of sulfuric acid generated in the pores of the plates is equal to the generation speed of the sulfuric acid, when the conversion rate of lead sulfate in the waste plates reaches 80% -90%, the activation voltage reaches 2.45-2.5V, and finally the rest lead sulfate is converted by charging with 0.05C low current for 5-10 h.
According to the invention, in the step (1), the waste positive plate contains 30-50 wt% of lead dioxide and 30-70 wt% of lead sulfate, and after the electrification activation, the activated positive plate obtained contains 99-100 wt% of lead dioxide and 0-1 wt% of lead sulfate; the waste negative plate contains 30-60 wt% of free lead, 5-10 wt% of lead oxide and 40-60 wt% of lead sulfate, and after the activation by the electrification, the obtained activated negative plate contains 99-100 wt% of free lead and 0-1 wt% of lead sulfate.
According to the present invention, in the step (2), the washing may be performed in a manner conventional in the art for removing the acid solution attached to the surfaces of the activated positive and negative electrode plates. For example, the rinsing may be repeated after soaking with pure water until the pH of the rinsing solution becomes neutral.
According to the invention, in the step (2), the drying is preferably performed under the condition of vacuum negative pressure, and the drying condition may include: the temperature is 60-80 deg.C, the pressure is-0.075 to-0.09 Mpa, and the time is 1-5 h.
According to the present invention, in the step (2), the gate paste separation may be performed by a method and an apparatus which are conventional in the art, and the present invention is not particularly limited thereto. For example, the active materials in the activated positive plate and the activated negative plate after drying are completely separated from the grid by a grid paste separator, and then the active materials and the grid are collected respectively.
According to the present invention, in the step (2), the positive active material obtained by grid paste separation has a lead dioxide content of 99 to 100 wt% and a lead sulfate content of 0 to 1 wt%; in the negative active material, the content of free lead is 90-100 wt%, the content of lead oxide is 0-10 wt%, and the content of lead sulfate is 0-1 wt%.
According to the invention, in step (3), the lead dioxide and free lead can be converted into lead oxide by the calcination. Preferably, the conditions of the firing may include: the temperature is 600-650 ℃, and the time is 1-3 h.
A second aspect of the invention provides a battery negative electrode powder produced by the method of the first aspect described above.
According to the invention, the average particle size of the battery negative electrode powder is 1-3 μm, and the content of PbO in the battery negative electrode powder is 99-100 wt%. The battery cathode powder provided by the invention has controllable particle size, crystal form and impurities, has good uniformity, and can ensure that the prepared lead-acid storage battery has excellent 100% DOD cycle life, low-temperature performance and high-current performance.
The third aspect of the invention provides the application of the negative electrode powder for the battery in the second aspect in the preparation of lead-acid storage batteries.
The battery cathode powder provided by the invention is used for preparing a lead-acid storage battery, the cycle life of 100% DOD can reach more than 650 times, and the low-temperature, large-current and charging acceptance capability of the battery cathode powder is equivalent to that of a conventional battery.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples, various raw materials used were commercially available without specific description.
Example 1
(1) Carrying out crushing and separation treatment on the waste lead-acid storage battery to obtain a waste positive plate and a waste negative plate, and connecting the waste positive plate with the positive electrode of a charger and connecting the waste negative plate with the negative electrode of the charger; then placing the waste positive plate and the waste negative plate which are connected with a charger in a dilute sulfuric acid solution with the temperature of 27 ℃ and the density of 1.05g/mL for standing for 1 h; after standing, starting a charger to electrify and activate the waste positive plate and the waste negative plate in the presence of the dilute sulfuric acid solution, wherein the activation mode is as follows: charging to a voltage of 2.45V by 0.15C current, and then charging for 5h by 0.05C current to obtain an activated positive plate and an activated negative plate;
(2) soaking the activated positive plate and the activated negative plate obtained in the step (1) in pure water, and repeatedly leaching until the pH value of leaching solution is neutral; then placing the mixture in a vacuum drying oven and drying the mixture for 5 hours under the conditions of 60 ℃ and-0.08 MPa; carrying out grid paste separation on the dried activated positive plate and the dried activated negative plate to obtain a positive active material, a negative active material and a lead grid;
(3) co-roasting the positive electrode active material and the negative electrode active material obtained in the step (2) for 3 hours at 600 ℃ by using a muffle furnace, cooling the roasted product to normal temperature, and then carrying out ball milling to obtain battery negative electrode powder with the average particle size of 1-3 mu m, which is recorded as S1.
The PbO content in S1 was tested to be 99.1 wt%.
Example 2
(1) Carrying out crushing and separation treatment on the waste lead-acid storage battery to obtain a waste positive plate and a waste negative plate, and connecting the waste positive plate with the positive electrode of a charger and connecting the waste negative plate with the negative electrode of the charger; then placing the waste positive plate and the waste negative plate which are connected with a charger in a dilute sulfuric acid solution with the temperature of 30 ℃ and the density of 1.08g/mL for standing for 1 h; after standing, starting a charger to electrify and activate the waste positive plate and the waste negative plate in the presence of the dilute sulfuric acid solution, wherein the activation mode is as follows: charging to a voltage of 2.48V by 0.15C current, and then charging for 8h by 0.05C current to obtain an activated positive plate and an activated negative plate;
(2) soaking the activated positive plate and the activated negative plate obtained in the step (1) in pure water, and repeatedly leaching until the pH value of leaching solution is neutral; then placing the mixture in a vacuum drying oven and drying the mixture for 2 hours under the conditions of 70 ℃ and-0.085 MPa; carrying out grid paste separation on the dried activated positive plate and the dried activated negative plate to obtain a positive active material, a negative active material and a lead grid;
(3) co-roasting the positive electrode active material and the negative electrode active material obtained in the step (2) at 620 ℃ for 2 hours by using a muffle furnace, cooling the roasted product to normal temperature, and then carrying out ball milling to obtain battery negative electrode powder with the average particle size of 1-3 mu m, which is recorded as S2.
The PbO content in S2 was tested to be 99.4 wt%.
Example 3
(1) Carrying out crushing and separation treatment on the waste lead-acid storage battery to obtain a waste positive plate and a waste negative plate, and connecting the waste positive plate with the positive electrode of a charger and connecting the waste negative plate with the negative electrode of the charger; then placing the waste positive plate and the waste negative plate which are connected with a charger in a dilute sulfuric acid solution with the temperature of 32 ℃ and the density of 1.1g/mL for standing for 1 h; after standing, starting a charger to electrify and activate the waste positive plate and the waste negative plate in the presence of the dilute sulfuric acid solution, wherein the activation mode is as follows: charging to a voltage of 2.5V by 0.15C current, and then charging for 10h by 0.05C current to obtain an activated positive plate and an activated negative plate;
(2) soaking the activated positive plate and the activated negative plate obtained in the step (1) in pure water, and repeatedly leaching until the pH value of leaching solution is neutral; then placing the mixture in a vacuum drying oven and drying the mixture for 1h under the conditions of 80 ℃ and-0.09 MPa; carrying out grid paste separation on the dried activated positive plate and the dried activated negative plate to obtain a positive active material, a negative active material and a lead grid;
(3) co-roasting the positive electrode active material and the negative electrode active material obtained in the step (2) at 650 ℃ for 1h by using a muffle furnace, cooling the roasted product to normal temperature, and then carrying out ball milling to obtain battery negative electrode powder with the average particle size of 1-3 mu m, which is recorded as S3.
The PbO content in S3 was tested to be 99.8 wt%.
Example 4
(1) Carrying out crushing and separation treatment on the waste lead-acid storage battery to obtain a waste positive plate and a waste negative plate, and connecting the waste positive plate with the positive electrode of a charger and connecting the waste negative plate with the negative electrode of the charger; then placing the waste positive plate and the waste negative plate which are connected with a charger in a dilute sulfuric acid solution with the temperature of 25 ℃ and the density of 1.06g/mL for standing for 0.5 h; after standing, starting a charger to electrify and activate the waste positive plate and the waste negative plate in the presence of the dilute sulfuric acid solution, wherein the activation mode is as follows: charging to a voltage of 2.48V by 0.15C current, and then charging for 8h by 0.05C current to obtain an activated positive plate and an activated negative plate;
(2) soaking the activated positive plate and the activated negative plate obtained in the step (1) in pure water, and repeatedly leaching until the pH value of leaching solution is neutral; then placing the mixture in a vacuum drying oven and drying the mixture for 2.5 hours under the conditions of 60 ℃ and-0.085 MPa; carrying out grid paste separation on the dried activated positive plate and the dried activated negative plate to obtain a positive active material, a negative active material and a lead grid;
(3) co-roasting the positive electrode active material and the negative electrode active material obtained in the step (2) at 630 ℃ for 2.5h by using a muffle furnace, cooling the roasted product to normal temperature, and then carrying out ball milling to obtain battery negative electrode powder with the average particle size of 1-3 mu m, wherein the powder is recorded as S4.
The PbO content in S4 was tested to be 99.6 wt%.
Comparative example 1
The procedure of example 1 was followed except that, in step (1), the activation regime used was: the 0.15C current was charged to a voltage of 2.3V followed by a 0.05C current charge of 5 h. Other conditions were the same as in example 1, and a battery negative electrode powder having an average particle diameter of 1 to 3 μm was obtained and was designated as D1.
The PbO content in D1 was tested to be 97.6 wt%.
Comparative example 2
The procedure of example 1 was followed except that, in step (1), the activation regime used was: the 0.15C current was charged to a voltage of 2.45V, followed by a 0.05C current charge of 3 h. Other conditions were the same as in example 1, and a battery negative electrode powder having an average particle diameter of 1 to 3 μm was obtained and was designated as D2.
The PbO content in D2 was tested to be 96.5 wt%.
Comparative example 3
A battery negative electrode powder having an average particle size of 2.2 μm was obtained as D3 in accordance with CN106252776B in example 1.
The PbO content in D3 was tested to be 75.8 wt%.
Comparative example 4
Crushing the waste positive plate and the waste negative plate, separating active substances, mixing and stirring or ball-milling the active substances and 5-15 wt% of dilute alkali liquor according to the mass ratio of 1:2 for 0.5-1.5h for desulfurization, carrying out solid-liquid separation after the reaction is finished to obtain desulfurized lead paste, roasting the desulfurized lead paste at 650-750 ℃ for 3h, and grinding to obtain battery negative electrode powder with the average particle size of 3.84 mu m, which is marked as D4.
The PbO content in D4 was tested to be 98.3 wt%.
Test example
The battery negative electrode powders S1-S4 and D1-D4 prepared in examples 1-4 and comparative examples 1-4 were used to prepare 12V 20Ah lead-acid batteries according to the conventional process, and the performance of the lead-acid batteries was evaluated. In the following test examples, the following test examples were carried out,
100% DOD cycle performance: testing according to the method specified in GB/T22199.1-2017;
1.8C high current performance: testing according to the method specified in GB/T T22199.1-2017;
-18 ℃ low temperature performance: the test was carried out according to the method specified in GB/T T22199.1-2017.
The test results are shown in table 1.
TABLE 1
It can be seen from table 1 that the battery negative electrode powder S1-S4 provided by the preparation method of the present invention can make the lead-acid storage battery have excellent performance in 100% DOD cycle performance, 1.8C large current performance, and-18 ℃ low temperature performance, and particularly, the cycle life of 100% DOD reaches more than 650 times, which is significantly improved compared with the battery negative electrode powder D3 and D4 prepared by the existing method.
In the activation process of comparative example 1, the 0.15C current was charged to a voltage of 2.3V, and the lower voltage resulted in incomplete conversion of lead sulfate of the positive electrode plate to lead dioxide and conversion of lead sulfate of the negative electrode plate to free lead, thereby making the performance of the lead-acid storage battery using the negative electrode powder D1 significantly inferior to the effect of the present invention.
In the activation process of comparative example 2, 0.05C current charging for 3 hours, the shorter charging time also resulted in incomplete conversion of lead sulfate of the positive electrode plate to lead dioxide and conversion of lead sulfate of the negative electrode plate to free lead, and thus the lead-acid storage battery produced using negative electrode powder D2 failed to obtain the effects of the present invention.
The method for preparing the battery cathode powder provided by the invention has the advantages of simple process flow, low chemical reagent consumption and low cost, is beneficial to the implementation of actual production, and can obviously prolong the cycle life of 100 percent DOD of the battery by using the recycled cathode powder for preparing the lead-acid storage battery.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of making a battery negative electrode powder, comprising:
(1) connecting a waste positive plate with a positive electrode of a charger, connecting a waste negative plate with a negative electrode of the charger, and then electrifying and activating the waste positive plate and the waste negative plate in the presence of acid liquor to obtain an activated positive plate and an activated negative plate;
(2) washing and drying the activated positive plate and the activated negative plate in sequence, and then separating grid paste to obtain a positive active material, a negative active material and a lead grid;
(3) and roasting the positive electrode active substance and the negative electrode active substance together, and grinding a roasted product to obtain the battery negative electrode powder.
2. The method according to claim 1, wherein, in step (1), the waste positive and negative electrode plates are left to stand in the acid solution before the energization activation;
preferably, the conditions of said resting comprise: the temperature is 0-50 ℃ and the time is 0.5-1 h.
3. A process as claimed in claim 1 or 2, wherein in step (1), the acid liquor is a dilute sulphuric acid solution;
preferably, the dilute sulfuric acid solution has a density of 1.05-1.1 g/mL.
4. The method according to any one of claims 1-3, wherein in step (1), the process of energizing activation comprises: charging to voltage of 2.45-2.5V with 0.15C current, and charging for 5-10h with 0.05C current.
5. The method according to any one of claims 1 to 3, wherein in step (2), the drying conditions comprise: the temperature is 60-80 deg.C, the pressure is-0.075 to-0.09 Mpa, and the time is 1-5 h.
6. The method according to any one of claims 1 to 3, wherein, in step (2),
the content of lead dioxide in the positive active material is 99-100 wt%, and the content of lead sulfate is 0-1 wt%;
the content of free lead in the negative active material is 90-100 wt%, the content of lead oxide is 0-10 wt%, and the content of lead sulfate is 0-1 wt%.
7. The method of any one of claims 1-3, wherein in step (3), the firing conditions comprise: the temperature is 600-650 ℃, and the time is 1-3 h.
8. A battery negative electrode powder prepared by the method of any one of claims 1 to 7.
9. The battery negative electrode powder according to claim 8, wherein the average particle diameter of the battery negative electrode powder is 1 to 3 μm, and the PbO content is 99 to 100 wt%.
10. Use of the battery negative electrode powder of claim 8 or 9 in the manufacture of a lead-acid battery.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1933233A (en) * | 2006-09-30 | 2007-03-21 | 李建德 | Valve controlling sealed lead-acid battery negative pole plate salt crystallization activation method |
| JP2009016324A (en) * | 2007-07-03 | 2009-01-22 | Mase Shunzo | Regenerating method for lead storage battery and its device |
| CN103184340A (en) * | 2011-12-31 | 2013-07-03 | 深圳市雄韬电源科技股份有限公司 | Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster |
| CN104393364A (en) * | 2014-11-13 | 2015-03-04 | 张家港智电芳华蓄电研究所有限公司 | Method for preparing PbO from waste lead-acid battery by using direct wet method |
| CN105406031A (en) * | 2015-12-08 | 2016-03-16 | 超威电源有限公司 | Negative electrode lead paste of lead-acid accumulator |
| CN105406143A (en) * | 2015-11-02 | 2016-03-16 | 扬州大学 | Method for preparing lead storage battery electrode plate from lead-bearing compound in waste lead storage battery as raw material |
| CN113481374A (en) * | 2021-07-13 | 2021-10-08 | 湘潭大学 | Self-coupling reaction method for lead and lead dioxide in waste lead paste |
-
2021
- 2021-10-21 CN CN202111229416.7A patent/CN114188531B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1933233A (en) * | 2006-09-30 | 2007-03-21 | 李建德 | Valve controlling sealed lead-acid battery negative pole plate salt crystallization activation method |
| JP2009016324A (en) * | 2007-07-03 | 2009-01-22 | Mase Shunzo | Regenerating method for lead storage battery and its device |
| CN103184340A (en) * | 2011-12-31 | 2013-07-03 | 深圳市雄韬电源科技股份有限公司 | Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster |
| CN104393364A (en) * | 2014-11-13 | 2015-03-04 | 张家港智电芳华蓄电研究所有限公司 | Method for preparing PbO from waste lead-acid battery by using direct wet method |
| CN105406143A (en) * | 2015-11-02 | 2016-03-16 | 扬州大学 | Method for preparing lead storage battery electrode plate from lead-bearing compound in waste lead storage battery as raw material |
| CN105406031A (en) * | 2015-12-08 | 2016-03-16 | 超威电源有限公司 | Negative electrode lead paste of lead-acid accumulator |
| CN113481374A (en) * | 2021-07-13 | 2021-10-08 | 湘潭大学 | Self-coupling reaction method for lead and lead dioxide in waste lead paste |
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