CN110931716B - Storage battery with low-voltage recharging performance and green plate lead paste - Google Patents
Storage battery with low-voltage recharging performance and green plate lead paste Download PDFInfo
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- CN110931716B CN110931716B CN201911150673.4A CN201911150673A CN110931716B CN 110931716 B CN110931716 B CN 110931716B CN 201911150673 A CN201911150673 A CN 201911150673A CN 110931716 B CN110931716 B CN 110931716B
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 40
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 28
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 28
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 24
- 238000007599 discharging Methods 0.000 claims abstract description 23
- 239000011505 plaster Substances 0.000 claims abstract description 23
- 239000006230 acetylene black Substances 0.000 claims abstract description 20
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 17
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 16
- 239000012498 ultrapure water Substances 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- QTKKZNYORNDROP-UHFFFAOYSA-N trifluoro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl)azanium Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[N+](F)(F)F QTKKZNYORNDROP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000052 comparative effect Effects 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- WFRUBUQWJYMMRQ-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WFRUBUQWJYMMRQ-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a storage battery with a recharging performance under a power shortage and green plate lead plaster, wherein the green plate lead plaster of the storage battery consists of positive and negative plate lead plasters, and the positive plate lead plaster is prepared from the following raw materials in parts by weight: 80-90 parts of lead powder, 2-5 parts of titanium monoxide, 1-2 parts of calcium hydrophosphate, 2-4 parts of modified carbon nanotube, 0.5-1 part of hydrofluoric acid, 0.5-1 part of fumed silica, 5-8 parts of ultrapure water and 6-9 parts of sulfuric acid; the negative plate lead paste is prepared from the following raw materials in parts by weight: 75-82 parts of lead powder, 0.2-0.6 part of superfine barium sulfate, 1.5-2.5 parts of dimethylbenzene, 6-10 parts of acetylene black, 4-6 parts of fullerene, 3-5 parts of modified carbon nanotube, 5-7 parts of ultrapure water and 6-9 parts of sulfuric acid. The storage battery with the under-voltage recharging performance prepared from the green plate lead plaster has the advantages of high recharging rate, namely good charging acceptance after discharging and long deep cycle life.
Description
Technical Field
The invention belongs to the field of storage batteries, and particularly relates to a storage battery with a recharging performance under a power shortage condition and green plate lead plaster.
Background
Batteries were invented in 1859 by planter (plantate) and have been in history for over a hundred years to date. The lead-acid storage battery has been invented since the invention is one of the storage battery varieties with the largest output and the widest application in the world due to the characteristics of low price, easily available raw materials, reliable performance, easy recovery, suitability for large-current discharge and the like, and particularly the application of the lead-acid storage battery in the automobile industry. In the starting process of the automobile, the lead-acid storage battery discharges, the battery is in a floating charge state, the discharging depth is shallow, and the battery belongs to a shallow recycling battery.
With the increasing demand of customers, automobile manufacturers increasingly install entertainment equipment, air conditioners, electric blankets and the like on vehicles in order to make automobiles more and more sold. If the entertainment equipment is improperly used, the service life of the storage battery is shortened, the engine of the vehicle is generally selected to be shut down in the processes of loading and unloading goods, waiting for people and the like, the vehicle-mounted lead-acid storage battery is used for supplying power to the entertainment equipment, an air conditioner and the like, so that the deep discharge of the battery occurs, the phenomenon of insufficient recharging amount due to the limitation of the self condition of the battery exists after the vehicle is started, and further, the battery is short-term in power shortage, and the service life is shortened.
Disclosure of Invention
The invention aims to solve the technical problem of providing a storage battery with the capacity of recharging under the condition of power shortage and green plate lead plaster.
The technical problem to be solved by the invention is realized by the following technical scheme:
the storage battery green plate lead plaster comprises positive and negative plate lead plasters:
the positive plate lead paste is prepared from the following raw materials in parts by weight: 80-90 parts of lead powder, 2-5 parts of titanium monoxide, 1-2 parts of calcium hydrophosphate, 2-4 parts of modified carbon nanotube, 0.5-1 part of hydrofluoric acid, 0.5-1 part of fumed silica, 5-8 parts of ultrapure water and 6-9 parts of sulfuric acid;
the negative plate lead paste is prepared from the following raw materials in parts by weight: 75-82 parts of lead powder, 0.2-0.6 part of superfine barium sulfate, 1.5-2.5 parts of dimethylbenzene, 6-10 parts of acetylene black, 4-6 parts of fullerene, 3-5 parts of modified carbon nanotube, 5-7 parts of ultrapure water and 6-9 parts of sulfuric acid.
As a most preferable scheme, the positive plate lead paste comprises the following raw materials in parts by weight: 85 parts of lead powder, 3 parts of titanium monoxide, 1.5 parts of calcium hydrophosphate, 3 parts of modified carbon nano tube, 0.8 part of hydrofluoric acid, 0.8 part of fumed silica, 6 parts of ultrapure water and 7 parts of sulfuric acid.
As a most preferable scheme, the negative plate lead paste comprises the following raw materials in parts by weight: 78 parts of lead powder, 0.4 part of superfine barium sulfate, 2 parts of dimethylbenzene, 8 parts of acetylene black, 5 parts of fullerene, 4 parts of modified carbon nano tube, 6 parts of ultrapure water and 8 parts of sulfuric acid.
Preferably, the density of sulfuric acid of the positive and negative electrode lead pastes is 1.30-1.40 g/cm3。
As a most preferred scheme, the sulfuric acid density of the positive and negative plate lead pastes is 1.32g/cm3。
Preferably, the negative plate lead paste has C as fullerene60A water-soluble fullerene.
As a preferable scheme, the preparation method of the modified carbon nanotube of the positive and negative plate lead pastes comprises the following steps: mixing 2-5 parts of perfluorooctyl ammonium sulfonate, 4-6 parts of sulfuric acid, 1-2 parts of vinyltriethoxysilane and 20-24 parts of carbon nano tube, uniformly stirring, drying at 130-150 ℃ for 1-1.5 hours under the protection of nitrogen, adding 3-6 parts of tetrachloroethane, drying at 100-120 ℃ for 0.6-1 hour under the protection of nitrogen, and finally grinding to obtain the modified carbon nano tube.
As a most preferable scheme, the preparation method of the modified carbon nanotubes of the positive and negative plate lead pastes comprises the following steps: mixing 3 parts of perfluorooctyl ammonium sulfonate, 5 parts of sulfuric acid, 1.5 parts of vinyl triethoxysilane and 22 parts of carbon nano tube, uniformly stirring, drying at 140 ℃ for 1.2 hours under the protection of nitrogen, adding 4 parts of tetrachloroethane, drying at 100-120 ℃ for 0.8 hour under the protection of nitrogen, and finally grinding to obtain the modified carbon nano tube.
As a preferable scheme, the preparation method of the positive plate lead paste comprises the following steps: dissolving gas-phase silicon dioxide into hydrofluoric acid in advance for later use; adding lead powder and 35-45 wt% of water into a paste mixer, uniformly stirring, adding titanium monoxide, calcium hydrophosphate and 55-65 wt% of water, uniformly stirring, adding a modified carbon nano tube, pre-dissolved fumed silica and hydrofluoric acid, finally adding sulfuric acid, rapidly and uniformly stirring at the temperature of 80-90 ℃, and discharging paste at the temperature of 45-55 ℃ to obtain the storage battery positive plate lead paste with the capacity of recharging under the power loss.
As a most preferable scheme, the preparation method of the positive plate lead paste comprises the following steps: dissolving gas-phase silicon dioxide into hydrofluoric acid in advance for later use; adding lead powder and 40wt% of water into a paste mixer, uniformly stirring, adding titanium dioxide, calcium hydrophosphate and 60wt% of water, uniformly stirring, adding a modified carbon nano tube, pre-dissolved fumed silica and hydrofluoric acid, finally adding sulfuric acid, rapidly and uniformly stirring at the temperature of 85 ℃, and discharging paste at the temperature of 50 ℃ to obtain the storage battery positive plate lead paste with the recharging performance under the power loss.
As a preferable scheme, the preparation method of the negative plate lead paste comprises the following steps: dissolving acetylene black and modified carbon nanotubes in xylene in advance for later use; adding lead powder and 35-45 wt% of water into a paste mixer, uniformly stirring, adding 55-65 wt% of water, superfine barium sulfate, fullerene, acetylene black dissolved in xylene in advance and modified carbon nanotubes, adding sulfuric acid while stirring, rapidly and uniformly stirring at the temperature of 65-75 ℃, and discharging paste at the temperature of 45-55 ℃ to obtain the storage battery negative plate lead paste with the capacity of recharging under the condition of power loss.
As a most preferable scheme, the preparation method of the negative plate lead paste comprises the following steps: dissolving acetylene black and modified carbon nanotubes in xylene in advance for later use; adding lead powder and 40wt% of water into a paste mixer, uniformly stirring, adding 60wt% of water, superfine barium sulfate, fullerene, acetylene black dissolved in dimethylbenzene in advance and modified carbon nano tubes, adding sulfuric acid while stirring, rapidly and uniformly stirring at the temperature of 70 ℃, and discharging paste at the temperature of 50 ℃ to obtain the storage battery negative plate lead paste with the capacity of recharging under the condition of power loss.
The utility model provides a battery with under insufficient voltage recharge performance, the raw plate diachylon of battery with under the insufficient voltage recharge performance be above-mentioned raw plate diachylon.
Has the advantages that: (1) according to the invention, the modified carbon nano tube and the fumed silica are added into the green plate lead paste to prepare the storage battery with excellent performance, so that the charging and discharging time of the storage battery can be accelerated, and the charging and discharging capacity of the storage battery is greatly improved; (2) the green plate lead paste has good improvement effect on the capacity and low-temperature starting performance of the battery; (3) the storage battery prepared from the cathode lead plaster can obviously improve the deep discharge cycle performance of the battery and prolong the service life of the storage battery; (4) the storage battery prepared from the electrode-forming lead paste has high recharging rate, namely good charging acceptance after discharging.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Lead plaster for green plate of storage battery
The storage battery green plate lead paste is prepared from the following materials in percentage by weight:
and (3) positive plate lead paste: 85 parts of lead powder, 3 parts of titanium monoxide, 1.5 parts of calcium hydrophosphate, 3 parts of modified carbon nanotube, 0.8 part of hydrofluoric acid, 0.8 part of fumed silica, 6 parts of ultrapure water and 7 parts of sulfuric acid;
and (3) negative plate lead plaster: 78 parts of lead powder, 0.4 part of superfine barium sulfate, 2 parts of dimethylbenzene, 8 parts of acetylene black, 5 parts of fullerene, 4 parts of modified carbon nano tube, 6 parts of ultrapure water and 8 parts of sulfuric acid.
The density of sulfuric acid of the positive and negative electrode lead pastes is 1.32g/cm3。
The fullerene of the negative electrode plate lead paste is C60A water-soluble fullerene.
The preparation method of the modified carbon nano tube of the positive and negative plate lead pastes comprises the following steps: mixing 3 parts of perfluorooctyl ammonium sulfonate, 5 parts of sulfuric acid, 1.5 parts of vinyl triethoxysilane and 22 parts of carbon nano tube, uniformly stirring, drying at 140 ℃ for 1.2 hours under the protection of nitrogen, adding 4 parts of tetrachloroethane, drying at 110 ℃ for 0.8 hour under the protection of nitrogen, and finally grinding to obtain the modified carbon nano tube.
The preparation method of the positive plate lead paste comprises the following steps: dissolving gas-phase silicon dioxide into hydrofluoric acid in advance for later use; adding lead powder and 40wt% of water into a paste mixer, uniformly stirring, adding titanium dioxide, calcium hydrophosphate and 60wt% of water, uniformly stirring, adding a modified carbon nano tube, pre-dissolved fumed silica and hydrofluoric acid, finally adding sulfuric acid, rapidly and uniformly stirring at the temperature of 85 ℃, and discharging paste at the temperature of 50 ℃ to obtain the storage battery positive plate lead paste with the recharging performance under the power loss.
The preparation method of the negative plate lead paste comprises the following steps: dissolving acetylene black, fullerene and modified carbon nano-tubes in xylene in advance for later use; adding lead powder and 40wt% of water into a paste mixer, uniformly stirring, adding 60wt% of water, superfine barium sulfate and acetylene black, fullerene and modified carbon nano tubes dissolved in dimethylbenzene in advance, adding sulfuric acid while stirring, rapidly and uniformly stirring at the temperature of 70 ℃, and discharging paste at the temperature of 50 ℃ to obtain the storage battery negative plate lead paste with the capacity of recharging under the condition of power loss.
The utility model provides a battery with under insufficient voltage recharge performance, the green plate diachylon of battery with under the insufficient voltage recharge performance is above-mentioned green plate diachylon.
Example 2
Lead plaster for green plate of storage battery
The difference between the embodiment 2 and the embodiment 1 is that the anode and cathode lead pastes have different formula proportions and the other parts are the same.
Positive plate lead paste
80 parts of lead powder, 5 parts of titanium monoxide, 1 part of calcium hydrophosphate, 4 parts of modified carbon nano tube, 0.5 part of hydrofluoric acid, 1 part of fumed silica, 5 parts of ultrapure water and 9 parts of sulfuric acid.
Negative plate lead plaster
75 parts of lead powder, 0.6 part of superfine barium sulfate, 1.5 parts of dimethylbenzene, 10 parts of acetylene black, 4 parts of fullerene, 5 parts of modified carbon nano tube, 5 parts of ultrapure water and 9 parts of sulfuric acid.
Example 3
Lead plaster for green plate of storage battery
The difference between the example 3 and the example 1 is that the formulation ratio of the positive and negative plate lead pastes is different, and the others are the same.
Positive plate lead paste
90 parts of lead powder, 2 parts of titanium monoxide, 2 parts of calcium hydrophosphate, 2 parts of modified carbon nano tube, 1 part of hydrofluoric acid, 0.5 part of fumed silica, 8 parts of ultrapure water and 6 parts of sulfuric acid.
Negative plate lead plaster
82 parts of lead powder, 0.2 part of superfine barium sulfate, 2.5 parts of dimethylbenzene, 6 parts of acetylene black, 6 parts of fullerene, 3 parts of modified carbon nano tube, 7 parts of ultrapure water and 6 parts of sulfuric acid.
Example 4
Lead plaster for green plate of storage battery
Example 4 differs from example 1 in the positive and negative plate lead paste preparation parameters, and is otherwise the same.
The preparation method of the positive plate lead paste comprises the following steps: dissolving gas-phase silicon dioxide into hydrofluoric acid in advance for later use; adding lead powder and 35wt% of water into a paste mixer, uniformly stirring, adding titanium dioxide, calcium hydrophosphate and 65wt% of water, uniformly stirring, adding a modified carbon nano tube, pre-dissolved fumed silica and hydrofluoric acid, finally adding sulfuric acid, rapidly and uniformly stirring at the temperature of 80 ℃, and discharging paste at the temperature of 55 ℃ to obtain the storage battery positive plate lead paste with the recharging performance under the power loss.
The preparation method of the negative plate lead paste comprises the following steps: dissolving acetylene black, fullerene and modified carbon nano-tubes in xylene in advance for later use; adding lead powder and 35wt% of water into a paste mixer, uniformly stirring, adding 65wt% of water, superfine barium sulfate and acetylene black, fullerene and modified carbon nano tubes dissolved in dimethylbenzene in advance, adding sulfuric acid while stirring, rapidly and uniformly stirring at the temperature of 65 ℃, and discharging paste at the temperature of 55 ℃ to obtain the storage battery negative plate lead paste with the capacity of recharging under the condition of power loss.
Example 5
Lead plaster for green plate of storage battery
Example 5 is different from example 1 in the preparation parameters of the positive and negative electrode lead pastes, and the other parameters are the same.
The preparation method of the positive plate lead paste comprises the following steps: dissolving gas-phase silicon dioxide into hydrofluoric acid in advance for later use; adding lead powder and 45wt% of water into a paste mixer, uniformly stirring, adding titanium dioxide, calcium hydrophosphate and 55wt% of water, uniformly stirring, adding a modified carbon nano tube, pre-dissolved fumed silica and hydrofluoric acid, finally adding sulfuric acid, rapidly and uniformly stirring at the temperature of 90 ℃, and discharging paste at the temperature of 45 ℃ to obtain the storage battery positive plate lead paste with the recharging performance under the power loss.
The preparation method of the negative plate lead paste comprises the following steps: dissolving acetylene black, fullerene and modified carbon nano-tubes in xylene in advance for later use; adding lead powder and 45wt% of water into a paste mixer, uniformly stirring, adding 55wt% of water, superfine barium sulfate and acetylene black, fullerene and modified carbon nano tubes dissolved in dimethylbenzene in advance, adding sulfuric acid while stirring, rapidly and uniformly stirring at the temperature of 75 ℃, and discharging paste at the temperature of 45 ℃ to obtain the storage battery negative plate lead paste with the capacity of recharging under the condition of power loss.
Example 6
Lead plaster for green plate of storage battery
Example 6 differs from example 1 in the sulfuric acid density, all other things being equal.
The density of the sulfuric acid is 1.40 g/cm3。
Comparative example 1
Lead plaster for green plate of storage battery
The difference between the comparative example 1 and the example 1 is the formula of the positive and negative plate lead pastes, and the positive and negative plate lead pastes do not contain the modified carbon nano tubes.
Comparative example 2
Lead plaster for green plate of storage battery
Comparative example 2 differs from example 1 in that the positive and negative plate pastes are different, and the unmodified carbon nanotubes are used in this example, and the other steps are the same.
Comparative example 3
Lead plaster for green plate of storage battery
Comparative example 3 differs from example 1 in the formulation of the positive plate lead paste, which does not contain fumed silica, and is otherwise the same.
Comparative example 4
Lead plaster for green plate of storage battery
Comparative example 4 is different from example 1 in the formulation of the negative plate lead paste, and the negative plate of this example does not contain fullerene, but the other examples are the same.
Comparative example 5
Comparative example 5 is different from example 1 in that the modified carbon nanotube preparation raw materials of the positive and negative electrode plate lead pastes are different, and the others are the same.
The preparation method of the modified carbon nano tube of the positive and negative plate lead pastes comprises the following steps: mixing 3 parts of potassium perfluorooctyl sulfonate, 5 parts of nitric acid, 1.5 parts of isobutyl triethoxysilane and 22 parts of carbon nano tube, uniformly stirring, drying at 140 ℃ for 1.2 hours under the protection of nitrogen, adding 4 parts of tetrachloromethane, drying at 110 ℃ for 0.8 hour under the protection of nitrogen, and finally grinding to obtain the modified carbon nano tube.
To further demonstrate the effect of the present invention, the following test methods were provided:
1. the method for testing the rated capacity of the storage battery comprises the following steps:
and connecting the battery with a load for discharging, placing the battery at a termination voltage according to a constant discharge rate, stopping discharging, and calculating the product of the discharge time and the discharge current to obtain the capacity of the battery.
2. The method for testing the recharging performance of the storage battery after deep discharge comprises the following steps:
under the condition of room temperature, the storage battery is fully charged, and the storage battery is fully discharged after the storage battery is fully charged,
and after the discharging is finished, immediately putting the storage battery into a low-temperature box or a low-temperature chamber with the temperature of-5 ℃ for 24h, charging the storage battery in the low-temperature box according to the voltage of 14-15V until the charging current is kept unchanged for 4h, recording the total charging ampere-hour (Ah), and enabling the charging capacity to be more than or equal to 30% Cn. 3. The deep cycle life testing method comprises the following steps:
(1) in a room temperature environment, the storage battery is charged conventionally and then discharged in a conventional capacity detection manner;
(2) rapidly charging the lead-acid battery discharged in the step (1) for 2 hours at a large current and a constant voltage, standing for 20-25 minutes, and then performing volume detection and discharging;
(3) and (3) performing small-current constant-voltage conventional charging for a long time after the charging and discharging in the step (2) are cycled for 10 times, then continuing to perform capacity detection discharging to detect the 2-hour capacity of the battery in the conventional charging state, so that the battery is cycled for 10 times, and performing the next group of cycle tests from the step (2) after one group of cycles is completed until the service life of the battery is terminated.
The performance of the batteries with the recharging performance under power loss and the general batteries prepared in the above examples and comparative examples was tested, and the test results are shown in table 1:
TABLE 1 results of testing the performance of the storage battery
The capacity recharge rate after deep discharge reflects the charge acceptance of the battery after deep discharge, and the larger the capacity recharge rate after deep discharge is, the better the deep discharge recharge performance is. As can be seen from the data in table 1, example 1 is the best technical solution, and by comparing example 1 with examples 2 and 3, it can be seen that if the proportion of the positive and negative plate lead pastes is different from that of example 1, the cycle life and the recharging rate are both significantly reduced; comparing example 1 with examples 4 and 5, it can be seen that if the positive and negative plate lead pastes are prepared by different methods from example 1, the cycle life and the recharging rate are both significantly reduced; comparing example 1 with example 6, it can be seen that if the sulfuric acid concentration is different from that of the examples, the cycle life and the recharge rate are both significantly reduced; comparing example 1 with comparative examples 1 and 2, it can be seen that the cycle life and the recharge rate of the modified carbon nanotube can be remarkably improved; comparing example 1 with comparative examples 3 and 4, it can be seen that fumed silica and fullerene can also improve cycle life and recharge rate; it can be seen from comparison between example 1 and comparative example 5 that the modified carbon nanotubes prepared from different raw materials have different properties of the green plate lead paste, and the storage battery prepared from the green plate lead paste of example 1 has better cycle life and recharge rate.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The storage battery green plate lead plaster is characterized by comprising positive and negative plate lead plasters:
the positive plate lead paste is prepared from the following raw materials in parts by weight: 80-90 parts of lead powder, 2-5 parts of titanium monoxide, 1-2 parts of calcium hydrophosphate, 2-4 parts of modified carbon nano tube, 0.5-1 part of hydrofluoric acid, 0.5-1 part of fumed silica, 5-8 parts of ultrapure water and 6-9 parts of sulfuric acid;
the negative plate lead plaster is prepared from the following raw materials in parts by weight: 75-82 parts of lead powder, 0.2-0.6 part of superfine barium sulfate, 1.5-2.5 parts of dimethylbenzene, 6-10 parts of acetylene black, 4-6 parts of fullerene, 3-5 parts of modified carbon nanotube, 5-7 parts of ultrapure water and 6-9 parts of sulfuric acid;
the preparation method of the modified carbon nano tube of the positive and negative plate lead pastes comprises the following steps: mixing 2-5 parts of perfluorooctyl ammonium sulfonate, 4-6 parts of sulfuric acid, 1-2 parts of vinyltriethoxysilane and 20-24 parts of carbon nano tube, uniformly stirring, drying at 130-150 ℃ for 1-1.5 hours under the protection of nitrogen, adding 3-6 parts of tetrachloroethane, drying at 100-120 ℃ for 0.6-1 hour under the protection of nitrogen, and finally grinding to obtain the modified carbon nano tube.
2. The green plate lead paste for storage batteries according to claim 1, wherein the positive plate lead paste is prepared from the following raw materials in parts by weight: 85 parts of lead powder, 3 parts of titanium monoxide, 1.5 parts of calcium hydrophosphate, 3 parts of modified carbon nano tube, 0.8 part of hydrofluoric acid, 0.8 part of fumed silica, 6 parts of ultrapure water and 7 parts of sulfuric acid.
3. The green plate diachylon of the storage battery as claimed in claim 1, wherein the negative plate diachylon is prepared from the following raw materials in parts by weight: 78 parts of lead powder, 0.4 part of superfine barium sulfate, 2 parts of dimethylbenzene, 8 parts of acetylene black, 5 parts of fullerene, 4 parts of modified carbon nano tube, 6 parts of ultrapure water and 8 parts of sulfuric acid.
4. The green plate diachylon of claim 1, wherein the sulfuric acid density of the positive and negative plate diachylons is 1.30-1.40 g/cm3。
5. The battery green sheet lead paste of claim 1, wherein the fullerene of the negative plate lead paste is C60A water-soluble fullerene.
6. The storage battery green plate lead paste as claimed in claim 1, wherein the preparation method of the modified carbon nanotubes of the positive and negative plate lead paste comprises the following steps: mixing 3 parts of perfluorooctyl ammonium sulfonate, 5 parts of sulfuric acid, 1.5 parts of vinyl triethoxysilane and 22 parts of carbon nano tube, uniformly stirring, drying at 140 ℃ for 1.2 hours under the protection of nitrogen, adding 4 parts of tetrachloroethane, drying at 100-120 ℃ for 0.8 hour under the protection of nitrogen, and finally grinding to obtain the modified carbon nano tube.
7. The battery green plate lead paste according to claim 1, wherein the preparation method of the positive plate lead paste comprises the following steps: dissolving gas-phase silicon dioxide into hydrofluoric acid in advance for later use; adding lead powder and 35-45 wt% of water into a paste mixer, uniformly stirring, adding titanium monoxide, calcium hydrophosphate and 55-65 wt% of water, uniformly stirring, adding a modified carbon nano tube, pre-dissolved fumed silica and hydrofluoric acid, finally adding sulfuric acid, rapidly and uniformly stirring at the temperature of 80-90 ℃, and discharging paste at the temperature of 45-55 ℃ to obtain the storage battery positive plate lead paste with the capacity of recharging under the power loss.
8. The battery green plate lead paste according to claim 1, wherein the negative plate lead paste is prepared by a method comprising the following steps: dissolving acetylene black and modified carbon nanotubes in xylene in advance for later use; adding lead powder and 35-45 wt% of water into a paste mixer, uniformly stirring, adding 55-65 wt% of water, superfine barium sulfate, fullerene, acetylene black dissolved in xylene in advance and modified carbon nanotubes, adding sulfuric acid while stirring, rapidly and uniformly stirring at the temperature of 65-75 ℃, and discharging paste at the temperature of 45-55 ℃ to obtain the storage battery negative plate lead paste with the capacity of recharging under the condition of power loss.
9. A storage battery with low-voltage recharging performance is characterized in that green plate lead paste is the green plate lead paste according to any one of claims 1 to 8.
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