A lead-acid battery using a titanium substrate grid and a method of manufacturing the same

Abstract

This invention discloses a lead-acid battery using a titanium substrate grid (hereinafter referred to as a titanium-based lead-acid battery) and its preparation method. The titanium substrate grid used in the titanium-based lead-acid battery includes a titanium-based positive electrode grid and a titanium-based negative electrode grid for preparing the positive and negative electrode plates. Both the titanium-based positive and negative electrode grids have a titanium / intermediate layer / lead sandwich structure, the difference being that the intermediate layer of the positive electrode grid is composed of a metal oxide with good conductivity and corrosion resistance; the intermediate layer of the negative electrode grid is composed of a conductive metal layer with good corrosion resistance. The intermediate layers of both the positive and negative electrode grids can prevent the titanium substrate from being oxidized and improve the conductivity between the titanium substrate and the surface lead metal layer. This titanium / intermediate layer / lead titanium-based positive and negative electrode grid structure has the characteristics of light weight, good corrosion resistance, good conductivity, and good binding with active materials. The energy density of the titanium-based lead-acid battery exceeds 70 Wh / kg.

Description

Technical Field

[0001] This invention relates to a lead-acid battery using a titanium substrate grid and its preparation method, belonging to the field of advanced lead-acid battery technology. Background Technology

[0002] As is well known, lead-acid batteries are one of the oldest and most widely used rechargeable batteries to date. Despite the challenges posed by high-energy rechargeable batteries, lead-acid batteries have become one of the most important energy storage batteries due to their mature technology, high safety, good low-temperature performance, low manufacturing cost, high recycling rate (up to 99%), and a sound manufacturing base. However, compared with advanced rechargeable batteries such as lithium-ion batteries, lead-acid batteries still have significant shortcomings: one is their low actual energy density, approximately 30-40 Wh / kg. -1 It only accounts for 123 Wh / kg of the theoretical specific energy. -1 The battery's energy density ranges from 24.4% to 32.5%, primarily due to low utilization of active electrode materials and the large mass of inactive lead grids, which account for 20-30% of the battery's weight. Secondly, corrosion and softening of the positive electrode grid are significant issues. During charging, the lead dioxide positive electrode is polarized to a high potential, causing the lead alloy positive electrode grid, primarily composed of lead, to oxidize into lead oxides. This corrosion and fracture prevents the grid from providing support for the active materials, leading to battery failure. Although the negative electrode grid is not in a high-potential environment, sulfuric acid from the electrolyte can enter the active materials and come into contact with the negative electrode grid, causing it to corrode as well. Therefore, improving the energy density of lead-acid batteries and solving the problem of grid corrosion are urgent priorities.

[0003] One effective way to improve the energy density of lead-acid batteries is to replace traditional lead-based grids with lightweight grids. It is believed that lead alloy grids form a corrosion layer between the grid and the battery active material, ensuring the bonding between the grid and the active material. Therefore, a layer of metallic lead is typically plated onto a lightweight material, which most realistically simulates a lead alloy grid. Examples include aluminum and carbon. Aluminum substrates, plated with lead using a melt-plating method, are commonly used for the negative electrode grids of lead-acid batteries; however, an aluminum oxide passivation film easily forms on the aluminum substrate surface. Carbon substrates have been extensively studied for grid materials, such as pitch carbon, honeycomb carbon, glassy carbon, and graphite, which are used directly or by plating a layer of metallic lead for both positive and negative electrode grids in lead-acid batteries. Although carbon substrates have good electrical conductivity, they inherently have low mechanical strength. Furthermore, even with a lead-plated coating, carbon-based positive electrode grids are easily oxidized.

[0004] Titanium and its alloys have attracted considerable interest due to their excellent electrical conductivity, low density, strong corrosion resistance, and high mechanical strength. Research has shown that only one-tenth the amount of titanium required for lead grids can be used to fabricate lead-acid batteries of the same capacity, thus reducing battery weight and increasing energy density. However, titanium readily forms a non-conductive titanium dioxide film on its surface under sulfuric acid and high-potential environments, preventing the titanium substrate from being directly used as the grid material. Traditionally, titanium / oxide coatings or titanium / oxide coatings / lead dioxide are used as the positive electrode current collector in lead-acid batteries. Examples include titanium / ruthenium dioxide grids, titanium / ruthenium dioxide / lead dioxide grids, titanium / tin dioxide grids, and titanium / tin-antimony coating / lead dioxide grids, all of which offer some corrosion resistance. Ruthenium dioxide has a low oxygen evolution overpotential, leading to decreased battery charge / discharge efficiency and severe self-discharge. While tin-antimony oxide coatings have a high oxygen evolution overpotential, the bonding between the grid and the active material is poor, causing the active material to easily detach during operation, resulting in battery failure. In addition, this titanium / oxide coating structure of the titanium substrate gate is not suitable for environments with negative electrode potential.

[0005] Chinese patent application 201010524211.7, "Lightweight Grid for Lead-Acid Battery and its Preparation Method," uses titanium powder as a substrate, which is then rolled together with litharge powder, lead powder, etc., to form the positive and negative electrode grids. In this method, the titanium matrix powder directly contacts sulfuric acid, causing the grid to fail rapidly. Chinese patent application 200610110234.7, "Foamed Titanium-Based Positive and Negative Electrode Grid Material for Lead-Acid Battery and its Manufacturing Method," uses foamed titanium as a substrate, then a silver plating layer as a conductive layer, and finally electroplated lead dioxide as the positive electrode grid and electroplated lead as the negative electrode grid. This positive electrode grid has poor adhesion to the battery active material, and the use of silver metal layers in the positive and negative electrode grids significantly increases the battery cost. Chinese patent applications 201410166118.1, "A method for preparing a titanium / titanium suboxide / lead composite substrate," and 201210295358.2, "Titanium-based titanium suboxide plate and its manufacturing method," both use titanium suboxide as an anti-corrosion coating. However, titanium suboxide will still turn into non-conductive titanium dioxide under sulfuric acid and positive electrode potential, making the grid prone to failure. In Chinese patent application 200910219598.2, "Ti-0.2Pd titanium alloy-based foamed lead negative electrode grid for lead-acid batteries," Ti-0.2Pd titanium alloy is used as the substrate. Due to the use of 20% precious metal palladium, the battery manufacturing cost is high, making it unsuitable for industrial production.

[0006] Research on improving the corrosion resistance of lead-acid battery grids mainly focuses on adding other components to the lead alloy. Chinese patent application 201710188541.5, "A lead-acid battery grid with a composite coating and its preparation method," describes an improvement in corrosion resistance by electro-oxidizing the lead alloy grid and then preparing a composite coating. Chinese patent application 201610452943.7, "Preparation method of lead-acid battery grid alloy containing lead-tin-rare earth-graphene," primarily improves corrosion resistance by adding rare earth elements and graphene to the lead grid alloy. Chinese patent application 201610531584.4, "A high-performance corrosion-resistant composite coated grid for lead-acid batteries and its preparation method," improves corrosion resistance by preparing a polymer conductive layer on the surface of the lead alloy grid.

[0007] In the aforementioned research on lead-acid battery grids, it is difficult to reconcile lightweight grids with corrosion resistance. Lightweight grid materials not only exhibit poor corrosion resistance but also generally have poor bonding with active materials, as is the case with titanium-based grids. Furthermore, most research on titanium-based grids focuses on titanium positive electrode grids. Metal oxide coatings are used to prevent passivation of the titanium substrate in titanium positive electrode grids. However, this method is not applicable to titanium negative electrode grids. This is because the metal oxide coating is reduced at negative electrode potentials; therefore, finding an anti-passivation coating for titanium negative electrode grids at negative potentials is of great significance. In addition, research on the corrosion resistance of lead-acid battery grids is primarily based on lead alloy grids, which does not significantly improve the battery's energy density. Moreover, it is difficult to find a lightweight material that can be applied to both positive and negative electrode grids simultaneously. It is difficult to solve both the battery's energy density and the grid's susceptibility to corrosion at the same time. Summary of the Invention

[0008] The purpose of this invention is to address the problems of unifying lightweight grid materials and corrosion resistance, poor bonding between lightweight grids and battery active materials, and simultaneous application of lightweight grid materials in both positive and negative plates, thereby improving the performance of lead-acid batteries. This invention provides a lead-acid battery using a titanium substrate grid.

[0009] This invention discloses a lead-acid battery using a titanium substrate grid, wherein the titanium substrate grid includes a titanium-based positive electrode grid and a titanium-based negative electrode grid. The titanium-based positive electrode grid is formed into a positive electrode plate by coating with positive lead paste, and the titanium-based negative electrode grid is formed into a negative electrode plate by coating with negative lead paste.

[0010] The titanium-based positive electrode grid is a sandwich structure consisting of a titanium metal substrate, an intermediate layer, and a lead metal layer on the surface. The titanium metal substrate is a flattened titanium metal or titanium alloy mesh, and the intermediate layer is a metal oxide with good conductivity and corrosion resistance. The metal oxide is one of tin-antimony oxide, ruthenium-titanium oxide, ruthenium-titanium oxide, or iridium-tin oxide, with the ratio of tin-antimony, ruthenium-titanium, and iridium-tin elements between 9:1 and 6:4, and the ratio of ruthenium-titanium-tin elements between 2:7:1 and 1:7:2. The metal oxide content is 10-20 mg / cm³. 2 The thickness of the titanium metal substrate is 0.2-1.0 mm, and the thickness of the lead metal layer is 50-200 μm.

[0011] The titanium-based negative electrode grid has a sandwich structure consisting of a titanium metal substrate, an intermediate layer, and a lead metal layer on the surface. The titanium metal substrate is a flattened titanium metal sheet or titanium alloy mesh. The intermediate layer is made of a corrosion-resistant conductive metal material. The conductive metal is copper, which is deposited onto the surface of the titanium metal substrate through sensitization, activation, and chemical deposition steps. The chemical deposition solution composition is: 10-40 g / L copper sulfate pentahydrate, 4-16 g / L formaldehyde, 10-30 g / L sodium hydroxide, 20-60 g / L potassium sodium tartrate, 40-80 g / L disodium EDTA, and 20-50 mg / L lead. 2,2'-Bipyridine, 10-30 mg / L potassium ferrocyanide; chemical deposition time of 6-10 hours, temperature of 40-60℃; titanium metal substrate thickness of titanium-based negative electrode grid of 0.2-1.0 mm; intermediate layer thickness of 10-40 μm; lead metal layer thickness of surface of 50-200 μm.

[0012] The present invention discloses a method for fabricating a lead-acid battery using a titanium substrate grid, the steps of which are as follows:

[0013] I. Preparation of Titanium-Based Positive Electrode Grid

[0014] (1) Surface pretreatment of titanium metal substrate, wherein the titanium metal substrate is a flattened titanium metal or titanium alloy mesh;

[0015] (2) An intermediate layer is prepared on the surface of a titanium substrate. The intermediate layer is composed of a metal oxide with good conductivity and corrosion resistance. The metal oxide is one of tin-antimony oxide, ruthenium-titanium oxide, ruthenium-titanium oxide, and iridium-tin oxide. The ratio of tin-antimony, ruthenium-titanium, and iridium-tin elements is between 9:1 and 6:4, and the ratio of ruthenium-titanium elements is between 2:7:1 and 1:7:2.

[0016] (3) Electrodeposit a lead metal layer on the titanium-based intermediate layer in step (2);

[0017] II. Preparation of Titanium-Based Anode Grid

[0018] (1) Surface pretreatment of titanium metal substrate; the titanium metal substrate is a flattened titanium metal sheet or titanium alloy mesh;

[0019] (2) An intermediate layer is prepared on the surface of a titanium substrate, wherein the intermediate layer is made of a corrosion-resistant conductive metal material; wherein the conductive metal is copper, and it is deposited on the surface of the titanium metal substrate according to the steps of sensitization, activation and chemical deposition.

[0020] (3) Electrodeposit a lead metal layer on the intermediate layer in step (2);

[0021] The chemical deposition solution in step (2) consists of: 10-40 g / L copper sulfate pentahydrate, 4-16 g / L formaldehyde, 10-30 g / L sodium hydroxide, 20-60 g / L potassium sodium tartrate, 40-80 g / L disodium EDTA, 20-50 mg / L 2,2'-bipyridine, and 10-30 mg / L potassium ferrocyanide; the chemical deposition time is 6-10 hours, and the temperature is 40-60℃.

[0022] III. Preparation of Titanium-Based Positive Electrode Plates

[0023] The prepared positive electrode lead paste was coated onto the titanium-based positive electrode grid according to the conventional lead-acid battery positive electrode paste coating process, and then cured according to the conventional curing process to obtain the titanium-based positive electrode plate.

[0024] IV. Preparation of Titanium-Based Negative Electrode Plates

[0025] The prepared lead paste was coated onto the titanium-based negative electrode grid according to the conventional lead-acid battery negative electrode coating process, and then cured according to the conventional negative electrode curing process to obtain the titanium-based negative electrode plate.

[0026] V. Assembly of Titanium Substrate Lead-Acid Battery

[0027] Titanium-based positive electrode plates and titanium-based negative electrode plates, along with separators and electrolytes, are assembled and formed using traditional battery manufacturing processes to produce titanium-based grid lead-acid batteries.

[0028] Preferably, in step one, the preparation of the titanium-based positive electrode grid, an intermediate layer is prepared on the surface of the titanium substrate by a thermal decomposition method, wherein the steps of the thermal decomposition method are as follows:

[0029] 1) Prepare an alcoholic solution of metal ions according to the proportion of metal elements in the metal oxide, wherein the alcohol is one of n-butanol, isobutanol, or n-propanol;

[0030] 2) Add an acid solution to the obtained alcohol solution to obtain a coating solution, wherein the acid is hydrochloric acid, nitric acid or acetic acid;

[0031] 3) Apply the coating solution obtained in step 2) onto the titanium substrate, dry at 80-150℃ for 5-15 minutes, and then thermally oxidize in air at 400-600℃ for 5-15 minutes.

[0032] 4) Repeat step 3) 10-20 times until the content of metal ions in the coating, calculated based on metal oxides, reaches 10-20 mg / cm³. 2 ;

[0033] 5) Sinter at 400-600℃ for 1-2 hours in air atmosphere to obtain a titanium matrix with a metal oxide intermediate layer.

[0034] Preferably, in step two, the preparation of the titanium-based negative electrode grid, the sensitization solution in the sensitization step is a hydrochloric acid solution of stannous chloride, the concentration of stannous chloride is 10-40 g / L, the concentration of hydrochloric acid is 8-36 g / L, and the sensitization time is 5-20 minutes.

[0035] Preferably, in step two, the preparation of the titanium-based negative electrode grid, the activation step is carried out in a silver nitrate solution containing ammonia, with the ammonia concentration being 0.23-2.3 g / L, the silver nitrate concentration being 2-8 g / L, and the activation time being 5-15 minutes.

[0036] Preferably, in the preparation of the titanium-based positive electrode grid in step one and the preparation of the titanium-based negative electrode grid in step two, the pretreatment steps of the titanium metal substrate surface include water washing, degreasing, and acid etching; the degreasing step is to clean the titanium metal substrate surface with a hot 10-30wt% sodium hydroxide solution; the acid etching step is to treat the titanium metal substrate surface with a 10-30wt% hydrochloric acid solution at 80-100℃.

[0037] Preferably, in step one (preparation of the titanium-based positive electrode grid) and step two (preparation of the titanium-based negative electrode grid), a lead metal layer is electrodeposited on the titanium-based intermediate layer, and the composition of the electrodeposition solution used is 100-200 g / L Pb. 2+ 30-80 g / L free acid, 2-10 g / L gel; electrodeposition conditions include: room temperature, current density of 10-40 mA / cm². 2 The electrodeposition time is 30-120 minutes; the free acid is one or more of boric acid, fluoroboric acid, fluorosilicic acid, and methanesulfonic acid; the glue is one or more of wood glue, peach gum, animal glue, and gelatin.

[0038] Preferably, in step one, the preparation of the titanium-based positive electrode grid, and in step two, the preparation of the titanium-based negative electrode grid, Pb 2+ It is added in the form of lead salts, which are one or more of lead fluoroborate, lead nitrate, lead methanesulfonate, lead chloride, and lead fluorosilicate.

[0039] Preferably, in the preparation of the titanium-based positive electrode plate in step three, the positive electrode lead paste consists of 100 parts lead powder, 0.1-0.3 parts colloidal graphite, 0.1-0.2 parts short fibers, 6-10 parts sulfuric acid, and 10-15 parts deionized water.

[0040] Preferably, in step four, the preparation of the titanium-based positive electrode plate, the lead paste consists of 100 parts lead powder, 0.5-1.5 parts barium sulfate, 0.1-0.3 parts humic acid, 0.1-0.4 parts acetylene black, 0.1-0.15 parts short fibers, 0.1-0.3 parts sodium lignosulfonate, 8-10 parts sulfuric acid, and 10-13 parts deionized water.

[0041] Beneficial effects of the present invention

[0042] (1) The titanium-based lead-acid battery provided by the present invention has an energy density exceeding 70Wh / kg. In the titanium substrate grid, the titanium substrate thickness is 0.2mm, and the thickness of the electrodeposited lead layer is tens of micrometers. Compared with the traditional lead alloy grid, the weight of the titanium substrate grid is reduced by 90%.

[0043] (2) The titanium-based lead-acid battery provided by this invention has good corrosion resistance of the titanium substrate grid, which solves the problem of short lifespan caused by easy corrosion of the grid in lead-acid batteries. The lifespan of the titanium substrate grid lead-acid battery is improved, thus broadening the application scenarios of lead-acid batteries.

[0044] (3) The titanium-based lead-acid battery provided by the present invention has a unique titanium / intermediate layer / lead sandwich structure for its grid. The intermediate layer ensures that the titanium substrate is not passivated by sulfuric acid, and the lead metal layer ensures the bonding between the titanium substrate grid and the battery active material, forming a continuous conductive structure. Attached Figure Description

[0045] Figure 1 This is a structural diagram of a titanium-based lead-acid battery.

[0046] Figure 2 This is a battery cycle life diagram for Example 1.

[0047] Figure 3 This is the discharge energy diagram of Example 3. Detailed Implementation

[0048] Example 1

[0049] This embodiment provides a titanium-based lead-acid battery, wherein the titanium substrate is a flattened titanium metal mesh, the positive electrode grid is a titanium / tin-antimony oxide interlayer / lead grid, and the negative electrode grid is a titanium / copper interlayer / lead grid.

[0050] The above-mentioned titanium-based lead-acid battery is prepared by the following method, including the following steps:

[0051] (1) Fabrication of titanium-based positive electrode grid

[0052] S1-1: A flattened titanium metal mesh with a thickness of 1 mm was used as the titanium metal substrate. The titanium metal substrate was pretreated by water washing, degreasing, and acid etching. After water washing, it was degreased in a hot 30 wt% sodium hydroxide solution, and then acid etched with a 30 wt% hydrochloric acid solution heated to 80°C to remove the oxide film on the surface of the titanium substrate.

[0053] S1-2: 10 mg / cm 2 The tin-antimony metal oxide content is prepared according to the required metal oxide concentration ratio to prepare an alcohol solution of metal ions. The metal ions are SnCl4·5H2O, SbCl3, and SnCl2. Then, a certain amount of hydrochloric acid is added to the alcohol solution to obtain a coating solution. The prepared coating solution is brushed onto the treated titanium substrate, dried at 150°C for 10 minutes, and then thermally oxidized at 600°C in air for 15 minutes. This process is repeated 10 times until the coating solution is completely consumed. Finally, the substrate is sintered at 600°C in air for 2 hours to obtain a titanium substrate with a tin-antimony oxide intermediate layer.

[0054] S1-3: A lead layer was prepared on the titanium substrate with the aforementioned tin-antimony oxide intermediate layer using electrodeposition. The thickness of the deposited lead metal layer was 100 μm, and the solution composition for the electrodeposition method was 100 g / L Pb. 2+ Pb 2+ The additives were lead fluoroborate, 30 g / L free fluoroborate, and 2 g / L wood glue. The electrodeposition conditions were: temperature 25℃, current density 30 mA / cm². 2 The electrodeposition time is 60 minutes.

[0055] (2) Fabrication of titanium-based negative electrode grid

[0056] S2-1: This step is also a pretreatment step for the titanium matrix, and is the same as S1-1, so it will not be described again.

[0057] S2-2: A copper intermediate layer was prepared on the pretreated titanium substrate using chemical deposition. The process followed sensitization, activation, and chemical deposition steps. The pretreated titanium substrate was sensitized in a stannous chloride hydrochloric acid solution (20 g / L stannous chloride, 40 mL / L hydrochloric acid) for 5 minutes. Next, the sensitized titanium substrate was activated in a silver nitrate solution containing ammonia (4 mL / L ammonia, 3 g / L silver nitrate) for 5 minutes. Then, a copper layer was chemically deposited. The chemical deposition solution consisted of 20 g / L copper sulfate pentahydrate, 10 mL / L formaldehyde, 12 g / L sodium hydroxide, 30 g / L potassium sodium tartrate (tetrahydrate), 45 g / L EDTA disodium salt (dihydrate), 25 mg / L 2,2'-bipyridine, and 5 mg / L potassium ferrocyanide. The chemical deposition time was 8 hours, and the deposition temperature was 40°C. A titanium matrix with a copper metal interlayer is obtained.

[0058] S2-3: A lead layer is prepared on the titanium substrate with the copper interlayer by electrodeposition. The steps are the same as in S1-3, except that the electrodeposition time is 120 minutes.

[0059] (3) Preparation of titanium-based positive electrode plate

[0060] A positive electrode lead paste was prepared according to the following proportions: 100 parts lead powder, 0.2 parts colloidal graphite, 0.125 parts short fiber, 8.8 parts sulfuric acid, and 11.5 parts deionized water. The positive electrode lead paste was then coated onto the titanium-based positive electrode grid prepared in step (1). After curing, a titanium substrate grid positive electrode plate was obtained.

[0061] (4) Preparation of titanium-based negative electrode plate

[0062] A negative electrode lead paste was prepared according to the following proportions: 100 parts lead powder, 0.8 parts barium sulfate, 0.2 parts humic acid, 0.18 parts acetylene black, 0.13 parts short fiber, 0.2 parts sodium lignosulfonate, 8.3 parts sulfuric acid, and 11.5 parts deionized water. The lead paste was then applied to the titanium-based negative electrode grid prepared in step (2), and after curing, a titanium-based negative electrode grid plate was obtained.

[0063] (5) Assembly of titanium substrate lead-acid battery

[0064] The titanium-based positive electrode plate and titanium-based negative electrode plate prepared in steps (3) and (4) are assembled with the separator electrolyte and then formed to obtain a titanium-based lead-acid battery.

[0065] Example 2

[0066] This embodiment provides a titanium-based lead-acid battery. The titanium substrate is a flattened titanium metal mesh, the positive electrode grid is a titanium / tin-antimony oxide interlayer / lead grid, and the negative electrode grid is a titanium / copper interlayer / lead grid. The difference from Embodiment 1 lies in the thickness of the lead metal layer on the positive and negative electrode grids. The specific steps are as follows:

[0067] The difference between this embodiment and Embodiment 1 lies in the thickness of the lead metal layer on the positive and negative electrode plates. Therefore, the similarities will not be repeated. The differences are as follows:

[0068] The electrodeposition time for step S1-3 is 120 minutes;

[0069] The electrodeposition time for step S2-3 is 60 minutes.

[0070] Example 3

[0071] This embodiment provides a titanium-based lead-acid battery. The titanium substrate is a flattened titanium metal mesh, the positive electrode grid is a titanium / tin-antimony oxide interlayer / lead grid, and the negative electrode grid is a titanium / copper interlayer / lead grid. The difference from Embodiment 1 lies in the flattened titanium metal mesh and the thickness of the lead layer. The specific steps are as follows:

[0072] The difference between this embodiment and Embodiment 1 lies in the thickness of the flattened titanium mesh and the thickness of the lead metal layer; therefore, the identical parts will not be repeated. The different steps are as follows:

[0073] In step S1-1, a flattened titanium metal mesh with a thickness of 0.2 mm is used as the titanium metal substrate.

[0074] The electrodeposition time for step S1-3 is 30 minutes.

[0075] The electrodeposition time for step S2-3 is 30 minutes.

[0076] This embodiment demonstrates the fabrication of a high-energy-density titanium-based lead-acid battery. In this embodiment, the grid was fabricated using an ultra-thin titanium substrate, with a total weight of 2g for the titanium substrate and grid, 21g for the negative electrode active material, 26g for the positive electrode active material, 16g for the electrolyte, and 5g for the casing, resulting in a total battery weight of 70g. At a 2-hour rate of 100% DOD, the battery exhibits a discharge energy of 5Wh and an energy density of 71Wh / kg.

[0077] Example 4

[0078] This embodiment provides a titanium-based lead-acid battery. The titanium substrate is a flattened titanium metal mesh, the positive electrode grid is a titanium / ruthenium titanium oxide interlayer / lead grid, and the negative electrode grid is a titanium / copper interlayer / lead grid. The difference from Embodiment 1 lies in the oxide interlayer of the positive electrode grid. The specific steps are as follows:

[0079] The difference between this embodiment and Embodiment 1 is that the oxide intermediate layer of the positive electrode grid is ruthenium titanium oxide. The similarities will not be repeated. The differences are as follows:

[0080] S1-2 at 20mg / cm 2 The content of the ruthenium titanium oxide intermediate layer is prepared according to the required metal oxide concentration ratio in an alcohol solution containing the corresponding metal ions. The metal ions are sourced from RuCl3·xH2O and tetrabutyl titanate. A certain amount of hydrochloric acid is then added to the alcohol solution to obtain a coating solution. The prepared coating solution is brushed onto the treated titanium substrate, dried at 80°C for 10 minutes, and then thermally oxidized at 400°C in air for 10 minutes. This process is repeated 20 times until the coating solution is completely consumed. Finally, the substrate is sintered at 400°C in air for 2 hours to obtain a titanium substrate with a ruthenium titanium oxide intermediate layer.

[0081] Example 5

[0082] This embodiment provides a titanium-based lead-acid battery. The titanium substrate is a flattened titanium metal mesh, the positive electrode grid is a titanium / ruthenium titanium tin oxide interlayer / lead grid, and the negative electrode grid is a titanium / copper interlayer / lead grid. The difference from Embodiment 1 lies in the positive electrode grid oxide interlayer, and the specific steps are as follows:

[0083] The difference between this embodiment and Embodiment 1 is that the intermediate layer of the positive electrode grid oxide is ruthenium titanium tin oxide. The remaining steps and methods are the same, so they will not be described in detail. The difference is:

[0084] S1-2 at 20mg / cm 2 The content of the ruthenium titanium tin oxide intermediate layer is prepared according to the required metal oxide concentration ratio in an alcohol solution containing the corresponding metal ions. The metal ions are sourced from RuCl3·xH2O, tetrabutyl titanate, and SnCl4·5H2O. A certain amount of hydrochloric acid is then added to the alcohol solution to obtain a coating solution. The prepared coating solution is brushed onto the treated titanium substrate, dried at 150°C for 10 minutes, and then thermally oxidized at 600°C for 15 minutes in an air atmosphere. This process is repeated 20 times until the coating solution is completely consumed. Finally, the substrate is sintered at 600°C in an air atmosphere for 2 hours to obtain a titanium substrate with a ruthenium titanium tin oxide intermediate layer.

[0085] Example 6

[0086] This embodiment provides a titanium-based lead-acid battery. The titanium substrate is a flattened titanium mesh, the positive electrode grid is a titanium / iridium tin oxide interlayer / lead grid, and the negative electrode grid is a titanium / copper interlayer / lead grid. The difference from Embodiment 1 lies in the positive electrode grid oxide interlayer. The specific steps are as follows:

[0087] The difference between this embodiment and Embodiment 1 is that the intermediate layer of the positive electrode grid oxide is an iridium-tin intermediate layer; the rest are the same, so they will not be described in detail. The difference is:

[0088] S1-2 at 20mg / cm 2 The content of the iridium-tin oxide intermediate layer is prepared according to the required metal oxide concentration ratio in an alcohol solution containing the corresponding metal ions. The metal ions are derived from chloroiridium acid and SnCl4·5H2O. A certain amount of hydrochloric acid is then added to the alcohol solution to obtain a coating solution. The prepared coating solution is brushed onto the treated titanium substrate, dried at 80°C for 15 minutes, and then thermally oxidized at 400°C in air for 15 minutes. This process is repeated 20 times until the coating solution is completely consumed. Finally, the substrate is sintered at 400°C in air for 2 hours to obtain a titanium substrate with an iridium-tin oxide intermediate layer.

[0089] Example 7

[0090] This embodiment provides a titanium-based lead-acid battery. The titanium substrate is a flattened titanium metal mesh, the positive electrode grid is a titanium / tin-antimony oxide interlayer / lead grid, and the negative electrode grid is a titanium / copper interlayer / lead grid. The difference from Embodiment 1 lies in the thickness of the copper metal interlayer of the negative electrode grid. The specific steps are as follows:

[0091] The difference between this embodiment and Embodiment 1 lies in the thickness of the intermediate layer of copper metal at the negative electrode gate; the rest are the same and will not be described in detail. The difference is:

[0092] In step S2-2, the chemical deposition time is 10 hours and the deposition temperature is 60℃.

[0093] Effect verification:

[0094] like Figure 1 The diagram shown illustrates the battery structure of the titanium-based lead-acid battery of this invention. This battery uses a titanium substrate grid, with lead dioxide as the positive electrode active material and lead as the negative electrode active material, and is assembled using traditional lead-acid battery technology. Figure 2 As shown, the battery life reached 400 cycles under simulated 2-hour rate discharge (DOD) conditions at 100% DOD. Figure 3 As shown, Example 3 uses an ultra-thin titanium substrate, the total mass of the titanium-based battery is 70g, the discharge energy of the battery is 5Wh, and the battery energy density reaches 71Wh / kg.

[0095] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A lead-acid battery using a titanium substrate grid, characterized in that, The titanium substrate grid includes a titanium-based positive electrode grid and a titanium-based negative electrode grid. The titanium-based positive electrode grid is formed into a positive electrode plate by coating with positive lead paste, and the titanium-based negative electrode grid is formed into a negative electrode plate by coating with negative lead paste. The titanium-based positive electrode grid is a sandwich structure consisting of a titanium metal matrix, an intermediate layer, and a lead metal layer on the surface. The titanium metal matrix is ​​a flattened titanium metal or titanium alloy mesh, and the intermediate layer is a metal oxide with good conductivity and corrosion resistance. The metal oxide is one of tin-antimony oxide, ruthenium-titanium oxide, ruthenium-titanium oxide, or iridium-tin oxide, with the ratio of tin-antimony, ruthenium-titanium, and iridium-tin elements between 9:1 and 6:4, and the ratio of ruthenium-titanium-tin elements between 2:7:1 and 1:7:

2. The metal oxide content is 10-20 mg / cm³. 2 The thickness of the titanium metal substrate is 0.2-1.0 mm, and the thickness of the lead metal layer is 50-200 μm. The titanium-based negative electrode grid has a sandwich structure consisting of a titanium metal substrate, an intermediate layer, and a lead metal layer on the surface. The titanium metal substrate is a flattened titanium metal sheet or titanium alloy mesh. The intermediate layer is made of a corrosion-resistant conductive metal material. The conductive metal is copper, which is deposited onto the surface of the titanium metal substrate through sensitization, activation, and chemical deposition steps. The chemical deposition solution composition is: 10-40 g / L copper sulfate pentahydrate, 4-16 g / L formaldehyde, 10-30 g / L sodium hydroxide, 20-60 g / L potassium sodium tartrate, 40-80 g / L disodium EDTA, 20-50 mg / L 2,2'-bipyridine, and 10-30 mg / L potassium ferrocyanide. The chemical deposition time is 6-10 hours, and the temperature is 40-60 ℃. The thickness of the titanium metal substrate in the titanium-based negative electrode grid is 0.2-1.0 mm, and the thickness of the intermediate layer is 10-40 mm. μm; the lead metal layer on the surface is 50-200 μm thick.

2. A method for preparing a lead-acid battery using a titanium substrate grid as described in claim 1, characterized in that, The steps of this method are as follows: I. Preparation of Titanium-Based Positive Electrode Grid (1) Surface pretreatment of titanium metal substrate, wherein the titanium metal substrate is a flattened titanium metal or titanium alloy mesh; (2) An intermediate layer is prepared on the surface of a titanium substrate. The intermediate layer is composed of a metal oxide with good conductivity and corrosion resistance. The metal oxide is one of tin-antimony oxide, ruthenium-titanium oxide, ruthenium-titanium oxide, and iridium-tin oxide. The ratio of tin-antimony, ruthenium-titanium, and iridium-tin elements is between 9:1 and 6:4, and the ratio of ruthenium-titanium elements is between 2:7:1 and 1:7:

2. (3) Electrodeposit a lead metal layer on the titanium-based intermediate layer in step (2); II. Preparation of Titanium-Based Anode Grid (1) Surface pretreatment of titanium metal substrate; the titanium metal substrate is a flattened titanium metal sheet or titanium alloy mesh; (2) An intermediate layer is prepared on the surface of a titanium substrate, wherein the intermediate layer is made of a corrosion-resistant conductive metal material; the conductive metal is copper, which is deposited on the surface of the titanium metal substrate according to the steps of sensitization, activation and chemical deposition. (3) Electrodeposit a lead metal layer on the intermediate layer in step (2); The chemical deposition solution in step (2) consists of: 10-40 g / L copper sulfate pentahydrate, 4-16 g / L formaldehyde, 10-30 g / L sodium hydroxide, 20-60 g / L potassium sodium tartrate, 40-80 g / L disodium EDTA, 20-50 mg / L 2,2'-bipyridine, and 10-30 mg / L potassium ferrocyanide; the chemical deposition time is 6-10 hours, and the temperature is 40-60 ℃. III. Preparation of Titanium-Based Positive Electrode Plates The prepared positive electrode lead paste was coated onto the titanium-based positive electrode grid according to the conventional lead-acid battery positive electrode paste coating process, and then cured according to the conventional curing process to obtain the titanium-based positive electrode plate. IV. Preparation of Titanium-Based Negative Electrode Plates The prepared lead paste was coated onto the titanium-based negative electrode grid according to the conventional lead-acid battery negative electrode coating process, and then cured according to the conventional negative electrode curing process to obtain the titanium-based negative electrode plate. V. Assembly of Titanium Substrate Lead-Acid Battery Titanium-based positive and negative electrode plates, along with separators and electrolytes, are assembled and formed using traditional battery manufacturing processes to produce titanium-based grid lead-acid batteries.

3. The method for preparing a lead-acid battery using a titanium substrate grid according to claim 2, characterized in that, In step one, the preparation of the titanium-based positive electrode grid involves preparing an intermediate layer on the surface of the titanium substrate via a thermal decomposition method. The steps of the thermal decomposition method are as follows: 1) Prepare an alcoholic solution of metal ions according to the proportion of metal elements in the metal oxide, wherein the alcohol is one of n-butanol, isobutanol, or n-propanol; 2) Add an acid solution to the obtained alcohol solution to obtain a coating solution, wherein the acid is hydrochloric acid, nitric acid or acetic acid; 3) Apply the coating solution obtained in step 2) onto the titanium substrate, dry at 80-150℃ for 5-15 minutes, and then thermally oxidize in air at 400-600℃ for 5-15 minutes. 4) Repeat step 3) 10-20 times until the content of metal ions in the coating, calculated based on metal oxides, reaches 10-20 mg / cm³. 2 ; 5) Sinter at 400-600℃ for 1-2 hours in air atmosphere to obtain a titanium matrix with a metal oxide intermediate layer.

4. The method for preparing a lead-acid battery using a titanium substrate grid according to claim 2, characterized in that, In step two, the preparation of the titanium-based negative electrode grid, the sensitization solution in the sensitization step is a hydrochloric acid solution of stannous chloride, with a concentration of stannous chloride of 10-40 g / L and a concentration of hydrochloric acid of 8-36 g / L, and a sensitization time of 5-20 minutes.

5. The method for preparing a lead-acid battery using a titanium substrate grid according to claim 2, characterized in that, In step two, the preparation of the titanium-based negative electrode grid, the activation step is carried out in a silver nitrate solution containing ammonia, with an ammonia concentration of 0.23-2.3 g / L and a silver nitrate concentration of 2-8 g / L, for a activation time of 5-15 minutes.

6. The method for preparing a lead-acid battery using a titanium substrate grid according to claim 2, characterized in that, In step one, the preparation of the titanium-based positive electrode grid, and step two, the preparation of the titanium-based negative electrode grid, the pretreatment steps of the titanium metal substrate surface include water washing, degreasing, and acid etching; the degreasing step is to clean the titanium metal substrate surface with a hot 10-30wt% sodium hydroxide solution; the acid etching step is to treat the titanium metal substrate surface with a 10-30wt% hydrochloric acid solution at 80-100 ℃.

7. The method for preparing a lead-acid battery using a titanium substrate grid according to claim 2, characterized in that, In step one, the preparation of the titanium-based positive electrode grid, and in step two, the preparation of the titanium-based negative electrode grid, a lead metal layer is electrodeposited on the titanium-based intermediate layer. The composition of the electrodeposition solution used is 100-200 g / L Pb. 2+ 30-80 g / L free acid, 2-10 g / L gel; electrodeposition conditions include: room temperature, current density of 10-40 mA / cm². 2 The electrodeposition time is 30-120 minutes; the free acid is one or more of boric acid, fluoroboric acid, fluorosilicic acid, and methanesulfonic acid; the glue is one or more of wood glue, peach gum, animal glue, and gelatin.

8. The method for preparing a lead-acid battery using a titanium substrate grid according to claim 7, characterized in that, In step one, the preparation of the titanium-based positive electrode grid, and in step two, the preparation of the titanium-based negative electrode grid, Pb 2+ It is added in the form of lead salts, which are one or more of lead fluoroborate, lead nitrate, lead methanesulfonate, lead chloride, and lead fluorosilicate.

9. The method for preparing a lead-acid battery using a titanium substrate grid according to claim 2, characterized in that, In step three, the preparation of the titanium-based positive electrode plate, the positive electrode lead paste consists of 100 parts lead powder, 0.1-0.3 parts colloidal graphite, 0.1-0.2 parts short fibers, 6-10 parts sulfuric acid, and 10-15 parts deionized water.

10. The method for preparing a lead-acid battery using a titanium substrate grid according to claim 2, characterized in that, In step four, the preparation of the titanium-based negative electrode plate consists of 100 parts lead powder, 0.5-1.5 parts barium sulfate, 0.1-0.3 parts humic acid, 0.1-0.4 parts acetylene black, 0.1-0.15 parts short fiber, 0.1-0.3 parts sodium lignosulfonate, 8-10 parts sulfuric acid, and 10-13 parts deionized water.

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