CN117855468B - High-rate negative electrode active material of lead-acid battery, and preparation method and application thereof - Google Patents
High-rate negative electrode active material of lead-acid battery, and preparation method and application thereof Download PDFInfo
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- CN117855468B CN117855468B CN202410257344.4A CN202410257344A CN117855468B CN 117855468 B CN117855468 B CN 117855468B CN 202410257344 A CN202410257344 A CN 202410257344A CN 117855468 B CN117855468 B CN 117855468B
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 56
- 239000002253 acid Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 159000000009 barium salts Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 16
- -1 uniformly mixing Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000002608 ionic liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229960002903 benzyl benzoate Drugs 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 239000004021 humic acid Substances 0.000 claims description 10
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
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- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 8
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- ALGZQMQWKPQOER-UHFFFAOYSA-N 1-butyl-3-methyl-2H-imidazole cyanocyanamide Chemical compound N#CNC#N.CCCCN1CN(C)C=C1 ALGZQMQWKPQOER-UHFFFAOYSA-N 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 11
- 230000019635 sulfation Effects 0.000 abstract description 10
- 238000005670 sulfation reaction Methods 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 9
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 4
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- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 16
- 229910001626 barium chloride Inorganic materials 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
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- 239000006229 carbon black Substances 0.000 description 8
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
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Abstract
The invention particularly discloses a high-rate negative electrode active material of a lead-acid battery, and a preparation method and application thereof. According to the invention, the C-B-Ti-IL is used for coating the lead-mixed material, so that the conductivity of the polar plate can be improved, the internal resistance of the battery can be reduced, the utilization rate of active substances can be improved, sulfation can be restrained, a barium salt-containing film layer is formed outside the coating layer through an electrostatic spinning technology, the film can react with electrolyte to generate barium sulfate, the film has a unit cell size similar to that of lead sulfate, the similar unit cell size structure can provide nucleation sites of lead sulfate in the discharging process, more and even nucleation sites are beneficial to reducing the size of lead sulfate particles of a discharging product, further the discharging internal resistance of the battery is reduced, the discharging capacity of the battery is improved, and meanwhile, the film can also improve the corrosion resistance of a lead electrode. The negative electrode material is applied to the lead-acid storage battery, so that the charge acceptance and the high-rate cycle life of the lead-acid storage battery can be effectively improved.
Description
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a high-rate negative electrode active material of a lead-acid battery, and a preparation method and application thereof.
Background
The lead-acid battery has the advantages of high capacity, low price, high single voltage, stable performance and wide use temperature range, so that the lead-acid battery is widely applied in the industries of electric power, communication, computers and the like, and is the storage battery with the largest yield and the widest application at present. At present, the energy provided by the lead-acid battery is 2-3 times cheaper than other types of secondary power supplies, and the recovery rate of the waste battery is high, so that the lead-acid battery can be used on a large scale on a new energy power automobile, and the market prospect is wide.
However, the service life of the lead-acid battery is obviously limited due to the problems of irreversible sulfation and hydrogen evolution of a negative plate, grid corrosion of a positive plate, sulfation of a negative active substance, battery degradation and the like of the current commercial lead-acid battery. The most important reason for the limited service life of the lead-acid battery is that a large number of irreversible and nonconductive PbSO 4 crystals are formed on the electrode plate through vulcanization in the use process, and the generation of a large number of PbSO 4 crystals can lead to the reduction of the content of active materials in the lead-acid battery, so that the phenomena of capacity and cycle life of the lead-acid battery are attenuated. Therefore, in order to avoid the phenomenon of attenuation of the cycle life of the lead-acid battery, the conventional method is to add nano materials such as carbon nanotubes, graphene and the like into the active material to inhibit the sulfation effect of the electrode plate so as to improve the cycle life of the lead-acid battery. Although the added nano carbon conductive paste can improve the cycle performance of the lead-acid storage battery to a certain extent, the lead-acid storage battery still has the problems of low discharge rate or short service life under the high-rate discharge working condition. Therefore, the development of a lead-acid anode material with better performance has great significance for the development of lead-acid batteries.
Disclosure of Invention
Aiming at the problems that the existing lead-acid battery is low in discharge rate or short in service life under the high-rate discharge working condition, the invention provides a high-rate negative electrode active material of the lead-acid battery, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
In a first aspect, the invention provides a preparation method of a high-rate negative electrode active material of a lead-acid battery, comprising the following steps:
Step a, adding lead powder, metal oxide, humic acid, concentrated nitric acid, benzyl benzoate, aromatic aldehyde, lignin and short fibers into absolute ethyl alcohol, uniformly mixing, roasting and ball-milling the mixed materials under inert atmosphere to obtain a lead-mixed material;
Step b, uniformly mixing a carbon material, polyvinylidene fluoride, boric acid, titanium dioxide and imidazole ionic liquid to obtain a carbon mixed material;
Step c, adding the carbon mixture into a lead-mixed material, uniformly mixing, coating the mixture on a substrate, and drying to obtain a negative electrode substrate;
Step d, uniformly mixing the soluble barium salt solution, polyacrylonitrile and acetone to obtain spinning solution;
And e, carrying out electrostatic spinning on the spinning solution, wherein a receiving plate is the negative electrode substrate, and obtaining the high-rate negative electrode active material.
Compared with the prior art, the preparation method of the high-rate negative electrode active material of the lead-acid battery provided by the invention has the advantages that firstly, C-B-Ti and imidazole ionic liquid are introduced to coat the lead-mixed material, wherein carbon can enable the negative electrode active material in the lead-acid battery to have enough porosity, meanwhile, carbon can also form a conductive network in the negative electrode active material to increase the conductivity of the negative electrode active material, the surface area of an electrode is increased, and the sufficient contact area between the active material and electrolyte is ensured; the imidazole ionic liquid and the B can inhibit corrosion of lead and precipitation of hydrogen, and improve the conductivity of the anode active material when charging and discharging are finished; the titanium dioxide can improve the stability of the interface between the negative electrode plate and the electrolyte, prevent the negative electrode material from sulfation, improve the utilization rate of the negative electrode active material, increase the electrochemical active area of the negative electrode active material, improve the capacity of the battery for providing higher current, increase the capacity of the battery and reduce the internal resistance, thereby solving the problems of easy sulfation and poor charge receiving capacity of the negative electrode active material; the coating layer formed by the C-B-Ti and the imidazole ionic liquid can effectively enhance the conductivity and charge acceptance of the cathode, and form a fine porous crystal structure in the reaction process, so that the hydrogen evolution reaction is effectively reduced, the reversibility of the cathode is improved, the sulfation is relieved, and the service life of the battery is remarkably prolonged.
Further, a film layer containing barium salt is formed outside the coating layer through an electrostatic spinning technology, the film layer can react with electrolyte to generate barium sulfate, the barium sulfate has a unit cell size similar to that of lead sulfate, the similar unit cell size structure can provide nucleation sites of the lead sulfate in a discharging process, more and even nucleation sites are beneficial to reducing the size of lead sulfate particles of a discharging product, further reducing the discharging internal resistance of a battery and improving the discharging capacity of the battery, and meanwhile, the film can also improve the corrosion resistance of a lead electrode.
According to the invention, the C-B-Ti-IL (ionic liquid) is used as an inner coating, and the fiber containing barium salt is used for outer coating, so that the problems of corrosive decay and hydrogen evolution of the negative electrode are effectively reduced, and meanwhile, the conductivity and charge acceptance of the negative electrode are improved, thereby remarkably improving the capacity of the battery and prolonging the service life of the battery.
Further, in the step a, the mass percentage of each raw material is as follows: 70% -75% of lead powder, 3% -5% of metal oxide, 0.1% -0.9% of humic acid, 1% -1.5% of concentrated nitric acid, 0.3% -0.5% of benzyl benzoate, 0.1% -1.2% of aromatic aldehyde, 0.2% -0.5% of lignin, 0.1% -0.3% of short fiber and the balance of absolute ethyl alcohol.
The concentrated nitric acid refers to commercial concentrated nitric acid with the mass fraction of about 68%.
The preferable raw materials of the lead-mixed material can enable the anode material to have better electrolyte permeability, improve the charge and discharge capacity of the electrode, inhibit the recrystallization of lead sulfate and prevent the growth of crystals, thereby playing a role in delaying the sulfation of the lead-acid battery, and effectively inhibiting the corrosion and hydrogen evolution reaction of the lead electrode, and further achieving the purpose of comprehensively prolonging the cycle life of the battery.
Further, in the step a, the roasting temperature is 800-1000 ℃ and the roasting time is 4-8 hours.
Further, in step a, the metal oxide is at least one of Bi2O3、Ga2O3、In2O3、MnO2、Al2O3、CuO or MgO.
Further, in the step a, the aromatic aldehyde is one or two of benzaldehyde and phenylacetaldehyde.
The preferred aromatic aldehydes inhibit lead electrode corrosion and slow down hydrogen evolution reactions.
In the step a, the short fibers are at least one of asbestos fibers, polyester fibers, glass fibers, acrylic short fibers or metal fibers, wherein the diameter of the short fibers is 20-60 mu m, and the length of the short fibers is 3-20 mm.
In the step a, the temperature is raised to 800-1000 ℃ by adopting a temperature programming mode, and the baking is carried out for 4-8 hours, wherein the temperature raising rate is 3-5 ℃/min.
The inert atmosphere in step a is provided by an inert gas, which may be an inert gas conventional in the art, such as argon, nitrogen, etc.
In the step b, the mass ratio of the carbon material to the polyvinylidene fluoride to the boric acid to the titanium dioxide to the imidazole ionic liquid is 0.8-1:0.7-0.9:0.001-0.004:0.002-0.005:0.003-0.006.
Preferably, in the step b, the carbon material is at least one of carbon black, graphite, activated carbon, single-walled carbon nanotubes or multi-walled carbon nanotubes.
More preferably, the carbon material is any two of carbon black, graphite, activated carbon, single-wall carbon nanotubes or multi-wall carbon nanotubes, and the mass ratio of the two carbon materials is 1:1-1:3.
Further, in the step b, the imidazole ionic liquid is at least one of 1-ethyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole bis-trifluoro-imide salt or 1-butyl-3-methylimidazole dicyano-ammonium salt.
The preferred ionic liquid can inhibit corrosion of the lead electrode and precipitation of hydrogen, and is also advantageous in improving the conductivity of the negative electrode active material. Through the cladding of the C-B-Ti-IL, the conductivity of the polar plate can be improved, the internal resistance of the battery can be reduced, the utilization rate of active substances can be improved, sulfation can be inhibited, and the method has important significance for prolonging the service life of a high-rate circulation process.
Further, in the step c, the addition amount of the carbon mixture is 50% -70% of the mass of the lead-mixed material.
Further, in step c, the coating amount of the coating was 0.001kg/cm 2~0.0015kg/cm2.
Further, in the step c, the substrate is aluminum foil.
Further, in the step d, the mass ratio of the barium salt solution to the polyacrylonitrile to the acetone is 3:0.1-0.3:0.7-0.9; the barium salt solution is a mixed solution of soluble barium salt, water and N, N-dimethylformamide, and the mass ratio of the soluble barium salt to the water to the N, N-dimethylformamide is 1-1.5:2:2.
In the step e, the usage amount of the spinning solution is 50% -70% of the mass of the lead-mixed material.
In the step e, the spinning voltage is 16 KV-25 KV, and the distance between the spray head and the negative substrate is 14 cm-16 cm.
In the step e, the advancing speed of the electrostatic spinning solution in the spinning process is 30 mu L/min-50 mu L/min, and the spinning temperature is 26-30 ℃.
The negative electrode active material prepared according to the present invention is pulverized into a powder-like substance at the time of use, and is adhered to at least one surface of the negative electrode plate after paste. The manner of adhesion includes any of coating, spraying, or spin coating.
The fiber film layer containing barium salt, which is coated outside the C-B-Ti-IL, can inhibit the growth and crystallization of PbSO 4, simultaneously reduce the resistance of the negative electrode, improve the corrosion resistance of the lead electrode and be beneficial to further improving the discharge multiplying power and the cycle life.
In a second aspect, the invention also provides a high-rate negative electrode active material, which is prepared by the preparation method of the high-rate negative electrode active material.
In a third aspect, the present invention also provides a negative electrode, including the high-rate negative electrode active material described above.
In a fourth aspect, the invention also provides the application of the high-rate negative electrode active material or the negative electrode in preparing a lead-acid storage battery.
In a fifth aspect, the present invention also provides a lead-acid battery comprising a high-rate negative electrode active material or the negative electrode described above.
The invention provides a superior negative electrode active material for the lead-acid storage battery, and the preparation method of the negative electrode active material has the advantages of wide raw material sources, low price, simple and feasible preparation process, capability of carrying out large-scale production, and wide application prospect, and opens up a new path for structural design and optimization of the negative electrode material of the high-performance lead-acid storage battery.
The invention also provides a battery module which comprises the lead-acid storage battery.
The negative electrode active material prepared by the invention effectively relieves the problems that the existing negative electrode material is easy to sulfate and hydrogen evolution, improves the penetrability between the negative electrode material and electrolyte solution, and can effectively improve the charge acceptance and the high-rate cycle life of the lead-acid storage battery when being applied to the lead-acid storage battery.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
The concentrated nitric acid used in the examples below refers to commercially available concentrated nitric acid having a mass fraction of about 68%.
The diameter of the glass fiber is 20-60 mu m, and the length is 3-20 mm.
Example 1
A method for preparing a negative active material, comprising the steps of:
Firstly, weighing 3.5g (70%) of lead powder, 0.15g (3%) of MgO, 0.005g (0.1%) of humic acid, 0.05g (1%) of concentrated nitric acid, 0.015g (0.3%) of benzyl benzoate, 0.005g (0.1%) of benzaldehyde, 0.01g (0.2%) of lignin and 0.005g (0.1%) of glass fiber, adding the mixture into 1.26g (25.2%) of absolute ethyl alcohol, ball milling the mixture for 5min at 2000rpm, then heating the mixture to 900 ℃ at a speed of 4 ℃/min under an inert atmosphere, roasting the mixture for 6h, cooling the mixture to room temperature, and ball milling the solid at 2500rpm for 5min to obtain a lead-mixed material;
Weighing 0.8g of carbon black and multi-wall carbon nano tubes in a glove box (O 2<0.0001%,H2 O < 0.0001%) according to a mass ratio of 1:1, adding 1mg of boric acid, 2 mg of TiO, 0.7g of polyvinylidene fluoride and 3mg of 1-ethyl-3-methylimidazole bis (trifluoro-imide) salt into a 30mL glass bottle, and stirring for 12 hours at 600r/min on a magnetic stirrer to obtain a carbon mixed material;
Step three, dripping the carbon mixture into the lead-mixed material according to 50% of the mass of the lead-mixed material, stirring for 1h, coating the mixture on an aluminum foil with the coating amount of 0.001kg/cm 2, and vacuum drying for 24h to obtain a negative electrode substrate;
Weighing barium chloride, deionized water and N, N-dimethylformamide according to a mass ratio of 1:2:2, and uniformly mixing to obtain a barium chloride solution; mixing 3g of barium chloride solution, 0.1g of polyacrylonitrile and 0.9g of acetone, performing ultrasonic dispersion for 40min, and stirring for 8h at 400r/min in a magnetic stirrer to obtain spinning solution;
And fifthly, adding the spinning solution into an electrostatic spinning instrument according to 50% of the mass of the lead-mixed material, carrying out electrospinning under 16KV voltage, keeping the distance between a spray head and a negative electrode substrate at 14cm, setting the propelling speed at 30 mu L/min, keeping the spinning temperature at 28 ℃, and drying the finally prepared sample in a vacuum drying chamber at 80 ℃ for 24 hours to obtain the negative electrode active material.
Example 2
A method for preparing a negative active material, comprising the steps of:
Firstly, weighing 3.5g (70%) of lead powder, 0.2g (4%) of MgO, 0.0225g (0.45%) of humic acid, 0.0625g (1.25%) of concentrated nitric acid, 0.02g (0.4%) of benzyl benzoate, 0.035g (0.7%) of benzaldehyde, 0.0175g (0.35%) of lignin and 0.01g (0.2%) of glass fiber, adding the mixture into 1.1325g (22.65%) of absolute ethyl alcohol, ball milling the mixture for 6min at 2000rpm, then heating the mixture to 800 ℃ at a speed of 3 ℃/min under an inert atmosphere, roasting the mixture for 8h, cooling the mixture to room temperature, and ball milling the solid at 2500rpm for 6min to obtain a lead-mixed material;
Weighing 0.9g of carbon black and multiwall carbon nanotubes together according to a mass ratio of 1:2 in a glove box (O 2<0.0001%,H2 O < 0.0001%), adding 2mg of boric acid, 2 mg of TiO, 0.8g of polyvinylidene fluoride and 4mg of 1-ethyl-3-methylimidazole hexafluorophosphate into a 30mL glass bottle, and stirring for 12h on a magnetic stirrer at 600r/min to obtain a carbon mixture;
Step three, dripping the carbon mixture into the lead-mixed material according to 60% of the mass of the lead-mixed material, stirring for 1h, coating the mixture on an aluminum foil, and vacuum drying for 24h to obtain a negative electrode substrate, wherein the coating amount is 0.00125kg/cm 2;
Weighing barium chloride, deionized water and N, N-dimethylformamide according to a mass ratio of 1.25:2:2, and uniformly mixing to obtain a barium chloride solution; mixing 3g of barium chloride solution, 0.2g of polyacrylonitrile and 0.8g of acetone, performing ultrasonic dispersion for 40min, and stirring for 10h at 400r/min in a magnetic stirrer to obtain spinning solution;
And fifthly, adding the spinning solution into an electrostatic spinning instrument according to 60% of the mass of the lead-mixed material, carrying out electrospinning under 20KV voltage, keeping the distance between a spray head and a negative electrode substrate at 15cm, setting the propelling speed at 40 mu L/min, keeping the spinning temperature at 28 ℃, and drying the finally prepared sample in a vacuum drying chamber at 80 ℃ for 24 hours to obtain the negative electrode active material.
Example 3
A method for preparing a negative active material, comprising the steps of:
Firstly, weighing 3.5g (70%) of lead powder, 0.25g (5%) of MgO, 0.045g (0.9%) of humic acid, 0.075g (1.5%) of concentrated nitric acid, 0.025g (0.5%) of benzyl benzoate, 0.06g (1.2%) of benzaldehyde, 0.025g (0.5%) of lignin and 0.015g (0.3%) of glass fiber, adding into 1.005g (20.1%) of absolute ethyl alcohol, ball milling for 5min at 2000rpm, then heating to 1000 ℃ at a speed of 5 ℃/min under an inert atmosphere, roasting for 4h, cooling to room temperature, and ball milling the solid at 2500rpm for 8min to obtain a lead-mixed material;
Weighing 1.0g of carbon black and multi-wall carbon nano tubes in a glove box (O 2<0.0001%,H2 O < 0.0001%) according to a mass ratio of 1:3, adding 4mg of boric acid, 2 mg of TiO, 0.9g of polyvinylidene fluoride and 6mg of 1-butyl-3-methylimidazole dicyano ammonium salt into a 30mL glass bottle, and stirring for 12 hours at 600r/min on a magnetic stirrer to obtain a carbon mixture;
Step three, dripping the carbon mixture into the lead-mixed material according to 70% of the mass of the lead-mixed material, stirring for 1h, coating the mixture on an aluminum foil, and vacuum drying for 24h to obtain a negative electrode substrate, wherein the coating amount is 0.0015kg/cm 2;
Weighing barium chloride, deionized water and N, N-dimethylformamide according to a mass ratio of 1.5:2:2, and uniformly mixing to obtain a barium chloride solution; mixing 3g of barium chloride solution, 0.3g of polyacrylonitrile and 0.7g of acetone, performing ultrasonic dispersion for 40min, and stirring for 12h at 400r/min in a magnetic stirrer to obtain spinning solution;
and fifthly, adding the spinning solution into an electrostatic spinning instrument according to 70% of the mass of the lead-mixed material, carrying out electrospinning under 25KV voltage, keeping the distance between a spray head and a negative electrode substrate at 16cm, setting the propelling speed at 50 mu L/min, keeping the spinning temperature at 28 ℃, and drying the finally prepared sample in a vacuum drying chamber at 80 ℃ for 24 hours to obtain the negative electrode active material.
Comparative example 1
This comparative example provides a method for preparing a negative electrode active material, which is different from example 2 in that TiO 2 in a carbon mixture is replaced with an equivalent amount of SiO 2, comprising the steps of:
Firstly, weighing 3.5g (70%) of lead powder, 0.2g (4%) of MgO, 0.0225g (0.45%) of humic acid, 0.0625g (1.25%) of concentrated nitric acid, 0.02g (0.4%) of benzyl benzoate, 0.035g (0.7%) of benzaldehyde, 0.0175g (0.35%) of lignin and 0.01g (0.2%) of glass fiber, adding the mixture into 1.1325g (22.65%) of absolute ethyl alcohol, ball milling the mixture for 6min at 2000rpm, then heating the mixture to 800 ℃ at a speed of 3 ℃/min under an inert atmosphere, roasting the mixture for 8h, cooling the mixture to room temperature, and ball milling the solid at 2500rpm for 6min to obtain a lead-mixed material;
Weighing 0.9g of carbon black and multiwall carbon nanotubes together according to a mass ratio of 1:2 in a glove box (O 2<0.0001%,H2 O < 0.0001%), adding 2mg of boric acid, 3mg of SiO 2, 0.8g of polyvinylidene fluoride and 4mg of 1-ethyl-3-methylimidazole hexafluorophosphate into a 30mL glass bottle, and stirring for 12h on a magnetic stirrer at 600r/min to obtain a carbon mixture;
Step three, dripping the carbon mixture into the lead-mixed material according to 60% of the mass of the lead-mixed material, stirring for 1h, coating the mixture on an aluminum foil, and vacuum drying for 24h to obtain a negative electrode substrate, wherein the coating amount is 0.00125kg/cm 2;
Weighing barium chloride, deionized water and N, N-dimethylformamide according to a mass ratio of 1.25:2:2, and uniformly mixing to obtain a barium chloride solution; mixing 3g of barium chloride solution, 0.2g of polyacrylonitrile and 0.8g of acetone, performing ultrasonic dispersion for 40min, and stirring for 10h at 400r/min in a magnetic stirrer to obtain spinning solution;
And fifthly, adding the spinning solution into an electrostatic spinning instrument according to 60% of the mass of the lead-mixed material, carrying out electrospinning under 20KV voltage, keeping the distance between a spray head and a negative electrode substrate at 15cm, setting the propelling speed at 40 mu L/min, keeping the spinning temperature at 28 ℃, and drying the finally prepared sample in a vacuum drying chamber at 80 ℃ for 24 hours to obtain the negative electrode active material.
Comparative example 2
This comparative example provides a method for preparing a negative electrode active material, which is different from example 2 in that barium chloride is replaced with an equivalent amount of calcium chloride, and specifically includes the steps of:
Firstly, weighing 3.5g (70%) of lead powder, 0.2g (4%) of MgO, 0.0225g (0.45%) of humic acid, 0.0625g (1.25%) of concentrated nitric acid, 0.02g (0.4%) of benzyl benzoate, 0.035g (0.7%) of benzaldehyde, 0.0175g (0.35%) of lignin and 0.01g (0.2%) of glass fiber, adding the mixture into 1.1325g (22.65%) of absolute ethyl alcohol, ball milling the mixture for 6min at 2000rpm, then heating the mixture to 800 ℃ at a speed of 3 ℃/min under an inert atmosphere, roasting the mixture for 8h, cooling the mixture to room temperature, and ball milling the solid at 2500rpm for 6min to obtain a lead-mixed material;
Weighing 0.9g of carbon black and multiwall carbon nanotubes together according to a mass ratio of 1:2 in a glove box (O 2<0.0001%,H2 O < 0.0001%), adding 2mg of boric acid, 2 mg of TiO, 0.8g of polyvinylidene fluoride and 4mg of 1-ethyl-3-methylimidazole hexafluorophosphate into a 30mL glass bottle, and stirring for 12h on a magnetic stirrer at 600r/min to obtain a carbon mixture;
Step three, dripping the carbon mixture into the lead-mixed material according to 60% of the mass of the lead-mixed material, stirring for 1h, coating the mixture on an aluminum foil, and vacuum drying for 24h to obtain a negative electrode substrate, wherein the coating amount is 0.00125kg/cm 2;
Weighing calcium chloride, deionized water and N, N-dimethylformamide according to a mass ratio of 1.25:2:2, and uniformly mixing to obtain a calcium chloride solution; mixing 3g of calcium chloride solution, 0.2g of polyacrylonitrile and 0.8g of acetone, performing ultrasonic dispersion for 40min, and stirring for 10h at 400r/min in a magnetic stirrer to obtain spinning solution;
And fifthly, adding the spinning solution into an electrostatic spinning instrument according to 60% of the mass of the lead-mixed material, carrying out electrospinning under 20KV voltage, keeping the distance between a spray head and a negative electrode substrate at 15cm, setting the propelling speed at 40 mu L/min, keeping the spinning temperature at 28 ℃, and drying the finally prepared sample in a vacuum drying chamber at 80 ℃ for 24 hours to obtain the negative electrode active material.
Comparative example 3
This comparative example provides a preparation method of a negative electrode active material, which is different from example 2 only in that the electrospinning is replaced by a spraying method, comprising the steps of:
Firstly, weighing 3.5g (70%) of lead powder, 0.2g (4%) of MgO, 0.0225g (0.45%) of humic acid, 0.0625g (1.25%) of concentrated nitric acid, 0.02g (0.4%) of benzyl benzoate, 0.035g (0.7%) of benzaldehyde, 0.0175g (0.35%) of lignin and 0.01g (0.2%) of glass fiber, adding the mixture into 1.1325g (22.65%) of absolute ethyl alcohol, ball milling the mixture for 6min at 2000rpm, then heating the mixture to 800 ℃ at a speed of 3 ℃/min under an inert atmosphere, roasting the mixture for 8h, cooling the mixture to room temperature, and ball milling the solid at 2500rpm for 6min to obtain a lead-mixed material;
Weighing 0.9g of carbon black and multiwall carbon nanotubes together according to a mass ratio of 1:2 in a glove box (O 2<0.0001%,H2 O < 0.0001%), adding 2mg of boric acid, 2 mg of TiO, 0.8g of polyvinylidene fluoride and 4mg of 1-ethyl-3-methylimidazole hexafluorophosphate into a 30mL glass bottle, and stirring for 12h on a magnetic stirrer at 600r/min to obtain a carbon mixture;
Step three, dripping the carbon mixture into the lead-mixed material according to 60% of the mass of the lead-mixed material, stirring for 1h, coating the mixture on an aluminum foil, and vacuum drying for 24h to obtain a negative electrode substrate, wherein the coating amount is 0.00125kg/cm 2;
Weighing barium chloride, deionized water and N, N-dimethylformamide according to a mass ratio of 1.25:2:2, and uniformly mixing to obtain a barium chloride solution; mixing 3g of barium chloride solution, 0.2g of polyacrylonitrile and 0.8g of acetone, performing ultrasonic dispersion for 40min, and stirring for 10h at 400r/min in a magnetic stirrer to obtain a precursor solution;
And fifthly, directly spraying the precursor solution onto the negative electrode substrate according to 60% of the mass of the lead-mixed material, and drying the finally prepared sample in a vacuum drying chamber at 80 ℃ for 24 hours to obtain the negative electrode active material.
Application examples
The negative electrode active materials prepared in examples 1-3 and comparative examples 1-3 were assembled into a lead-acid battery by a conventional welding method of "one negative electrode and two positive electrodes", and the positive electrode was a lead dioxide positive electrode plate. The preparation method of the negative electrode comprises the following steps:
Crushing the negative electrode active materials prepared in examples 1-3 and comparative examples 1-3, weighing 4g of the crushed negative electrode active material, adding 2g of deionized water and 2g of 98% concentrated sulfuric acid, uniformly stirring, coating the mixture on a lead-tin-calcium grid with the size of 69mm multiplied by 38mm multiplied by 2mm, compacting the lead-tin-calcium grid on a press for 2-4 min under the pressure of 16MPa, and curing the compacted lead-tin-calcium grid in an oven with the temperature of 60 ℃ and the humidity of 90% for 24h to obtain a negative plate.
Ultrafine glass wool (AMG diaphragm) is adopted between the positive plate and the negative plate, and the electrolyte is sulfuric acid solution with the density of 1.28 g/ml.
The negative electrode active materials prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for porosity (BET test), and the results are shown in table 1.
And placing the assembled lead-acid battery on a Shenzhen Xinweil BTS-5V6A battery test system for electrochemical performance test, wherein the test temperature is 25 ℃, and the test electrochemical window is 0V-2.5V.
The initial discharge capacity, the capacity retention after 200 cycles of long-cycle discharge, and the battery duration after high-rate discharge (5 c, 1c=160 mAh/g) are shown in table 1.
TABLE 1
The result shows that the anode active material prepared by the embodiment of the invention has higher porosity, is beneficial to improving the permeability of electrolyte and improving the charge-discharge capacity of an electrode, and the C-B-Ti-IL and the barium salt-containing coating layer can effectively inhibit the growth of lead sulfate particles, inhibit the sulfation of anode substances and improve the utilization rate of anode active substances, and simultaneously can effectively inhibit the corrosion of lead electrodes and reduce hydrogen evolution reaction, thereby being beneficial to improving the high-rate cycle life and having very important significance for the development of lead-acid batteries.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the high-rate negative electrode active material of the lead-acid battery is characterized by comprising the following steps of:
Step a, adding lead powder, metal oxide, humic acid, concentrated nitric acid, benzyl benzoate, aromatic aldehyde, lignin and short fibers into absolute ethyl alcohol, uniformly mixing, roasting and ball-milling the mixed materials under inert atmosphere to obtain a lead-mixed material;
Step b, uniformly mixing a carbon material, polyvinylidene fluoride, boric acid, titanium dioxide and imidazole ionic liquid to obtain a carbon mixed material;
Step c, adding the carbon mixture into a lead-mixed material, uniformly mixing, coating the mixture on a substrate, and drying to obtain a negative electrode substrate;
Step d, uniformly mixing the soluble barium salt solution, polyacrylonitrile and acetone to obtain spinning solution;
And e, carrying out electrostatic spinning on the spinning solution, wherein a receiving plate is the negative electrode substrate, and obtaining the high-rate negative electrode active material.
2. The method for preparing the high-rate negative electrode active material of the lead-acid battery according to claim 1, wherein in the step a, the mass percentage of each raw material is as follows: 70% -75% of lead powder, 3% -5% of metal oxide, 0.1% -0.9% of humic acid, 1% -1.5% of concentrated nitric acid, 0.3% -0.5% of benzyl benzoate, 0.1% -1.2% of aromatic aldehyde, 0.2% -0.5% of lignin, 0.1% -0.3% of short fiber and the balance of absolute ethyl alcohol; and/or
In the step a, the roasting temperature is 800-1000 ℃ and the roasting time is 4-8 hours.
3. The method for preparing a high-rate negative active material for a lead-acid battery according to claim 1 or 2, wherein in the step a, the metal oxide is at least one of Bi2O3、Ga2O3、In2O3、MnO2、Al2O3、CuO or MgO; and/or
In the step a, the aromatic aldehyde is one or two of benzaldehyde and phenylacetaldehyde; and/or
In the step a, the short fibers are at least one of asbestos fibers, polyester fibers, glass fibers, acrylic short fibers or metal fibers, wherein the diameter of the short fibers is 20-60 mu m, and the length of the short fibers is 3-20 mm; and/or
In the step a, the temperature is raised to 800-1000 ℃ by adopting a temperature programming mode, and the baking is carried out for 4-8 hours, wherein the temperature raising rate is 3-5 ℃/min.
4. The method for preparing the high-rate negative electrode active material of the lead-acid battery according to claim 1, wherein in the step b, the mass ratio of the carbon material to the polyvinylidene fluoride to the boric acid to the titanium dioxide to the imidazole ionic liquid is 0.8-1:0.7-0.9:0.001-0.004:0.002-0.005:0.003-0.006; and/or
In the step b, the imidazole ionic liquid is at least one of 1-ethyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole bis-trifluoro-imide salt or 1-butyl-3-methylimidazole dicyano-ammonium salt; and/or
In the step c, the addition amount of the carbon mixture is 50% -70% of the mass of the lead-mixed material; and/or
In step c, the coating amount of the coating is 0.001kg/cm 2~0.0015kg/cm2; and/or
In the step c, the substrate is aluminum foil.
5. The method for preparing the high-rate negative electrode active material of the lead-acid battery according to claim 1, wherein in the step d, the mass ratio of the barium salt solution to the polyacrylonitrile to the acetone is 3:0.1-0.3:0.7-0.9; the barium salt solution is a mixed solution of soluble barium salt, water and N, N-dimethylformamide, and the mass ratio of the soluble barium salt to the water to the N, N-dimethylformamide is 1-1.5:2:2; and/or
In the step e, the using amount of the spinning solution is 50% -70% of the mass of the lead-mixed material; and/or
In the step e, the spinning voltage is 16 KV-25 KV, and the distance between the spray nozzle and the negative electrode substrate is 14 cm-16 cm.
6. The high-rate negative electrode active material for a lead-acid battery, which is characterized by being prepared by the preparation method of the high-rate negative electrode active material for the lead-acid battery according to any one of claims 1-5.
7. A negative electrode comprising the high-rate negative electrode active material for a lead-acid battery according to claim 6.
8. Use of the high-rate negative electrode active material of a lead-acid battery according to claim 6 or the negative electrode according to claim 7 for the preparation of a lead-acid battery.
9. A lead-acid battery comprising the high-rate negative electrode active material for a lead-acid battery according to claim 6 or the negative electrode according to claim 7.
10. A battery module comprising the lead acid battery of claim 9.
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