A positive electrode and a battery containing the positive electrode

Abstract

The present invention relates to a positive electrode and a battery containing the positive electrode. Specifically, the present invention provides a positive electrode comprising a positive electrode active material, wherein the positive electrode active material comprises Hg2O7Sb2. Batteries prepared with the positive electrode of the present invention exhibit excellent energy density, cutoff voltage, safety, and other performance.

Description

Technical Field

[0001] The present invention relates to the field of batteries, and in particular to a positive electrode and a battery containing the positive electrode. Background Art

[0002] Batteries are widely used in production and life, and existing batteries are mainly lead-acid batteries and lithium batteries.

[0003] The positive and negative electrodes of lead-acid batteries are based on a lead alloy. The active material primarily consists of lead powder, sulfuric acid, and additives. The active material is applied to the lead-based grid and cured under certain temperature and humidity conditions to form green plates. Lead-acid batteries are manufactured using semi-finished materials such as plastic shells, plates, and separators, which are assembled and charged. However, the positive active material in lead-acid batteries has drawbacks such as low energy density (100Ah / kg).

[0004] The positive and negative electrodes of lithium batteries use aluminum film and copper film as current collectors respectively. The positive and negative electrode slurries prepared according to process requirements are coated on the current collectors. After drying and rolling, the tabs are made. Finally, the separator and casing are selected for assembly and charging to make lithium-ion batteries. However, lithium-ion batteries have poor safety performance, high production environment requirements and high costs.

[0005] Therefore, there is a need in the art to develop a battery with excellent performance. Summary of the Invention

[0006] The purpose of the present invention is to develop a battery with excellent energy density, cut-off voltage, safety and other properties.

[0007] A first aspect of the present invention provides a positive electrode, wherein the positive electrode comprises a positive electrode active material, and the positive electrode active material comprises Hg2O7Sb2.

[0008] Preferably, the positive electrode comprises a battery positive electrode.

[0009] Preferably, the battery comprises a primary battery or a secondary battery.

[0010] Preferably, the positive electrode active material further contains platinum oxide.

[0011] Preferably, the positive electrode active material contains Hg2O7Sb2 and platinum oxide.

[0012] Preferably, the positive electrode active material is coated on the surface of the inert material.

[0013] Preferably, the inert material comprises an inert material sheet, an inert material rod or an inert material stick.

[0014] Preferably, the inert material comprises graphite.

[0015] Preferably, the inert material comprises graphite sheets, graphite rods or graphite rods.

[0016] Preferably, the positive electrode comprises a positive electrode active material and an inert material, and the positive electrode active material is coated on the surface of the inert material.

[0017] Preferably, the thickness of the inert material is 0.05-0.5 mm, more preferably 0.05-0.3 mm, more preferably 0.05-0.15 mm, and even more preferably 0.08-0.12 mm.

[0018] Preferably, the Hg2O7Sb2 is 48-58 parts by weight, more preferably 50-55 parts by weight, more preferably 51-53 parts by weight, and even more preferably 52 parts by weight.

[0019] Preferably, the platinum oxide is 0.5-8 parts by weight, more preferably 1-6 parts by weight, more preferably 1-5 parts by weight, more preferably 2-3 parts by weight, and more preferably 2.5 parts by weight.

[0020] Preferably, the weight ratio of the Hg2O7Sb2 to the platinum oxide is 10-30:1, preferably 15-25:1, more preferably 18-23:1, more preferably 20-22:1, and most preferably 20.8:1.

[0021] A second aspect of the present invention provides a method for preparing the positive electrode according to the first aspect of the present invention, the method comprising:

[0022] (1) Hg2O7Sb2 and platinum oxide are mixed, and a solvent is added to the mixture to form a positive electrode slurry. The positive electrode slurry is coated on an inert material, solidified, and then dried to obtain a positive electrode.

[0023] Preferably, the Hg2O7Sb2 is 48-58 parts by weight, more preferably 50-55 parts by weight, more preferably 51-53 parts by weight, and even more preferably 52 parts by weight.

[0024] Preferably, the platinum oxide is 0.5-8 parts by weight, more preferably 1-6 parts by weight, more preferably 1-5 parts by weight, more preferably 2-3 parts by weight, and more preferably 2.5 parts by weight.

[0025] Preferably, the solvent comprises N-methylpyrrolidone.

[0026] Preferably, the solvent is 28-35 parts by weight, more preferably 30-34 parts by weight, and more preferably 32 parts by weight.

[0027] Preferably, the weight ratio of the Hg2O7Sb2 to the platinum oxide is 10-30:1, preferably 15-25:1, more preferably 18-23:1, more preferably 20-22:1, and most preferably 20.8:1.

[0028] Preferably, the weight ratio of the solvent to the platinum oxide is 5-25:1, more preferably 5-20:1, more preferably 10-15:1, more preferably 12-14:1, and most preferably 12.8:1.

[0029] Preferably, the coating amount of the positive electrode slurry on the surface area of the inert material is 0.5g / 100cm 2 Up to 2.5g / 100cm 2 , preferably 1g / 100cm 2 Up to 2g / 100cm 2 , preferably 1.2g / 100cm 2 Up to 1.8g / 100cm 2 , preferably 1.4g / 100cm 2 Up to 1.6g / 100cm 2 , optimally 1.5g / 100cm 2 .

[0030] Preferably, the curing temperature is 10-40°C, more preferably 10-30°C, more preferably 20-30°C, and most preferably 23-27°C.

[0031] Preferably, the curing time is 40-60 hours, more preferably 40-55 hours, more preferably 45-52 hours, and most preferably 46-50 hours.

[0032] Preferably, the drying temperature is 70-100°C, more preferably 70-90°C, more preferably 75-85°C, and most preferably 78-82°C.

[0033] Preferably, the drying time is 10-16 hours, more preferably 10-14 hours, and most preferably 11-13 hours.

[0034] Preferably, the coating amount of the positive electrode slurry on the surface area of the inert material is 1.3-1.7 g / 100 cm 2 , preferably 1.5g / 100cm 2 .

[0035] Preferably, the method comprises:

[0036] (1) After mixing 50-54 parts by weight of Hg2O7Sb2 and 2.3-2.7 parts by weight of platinum oxide, 30-34 parts by weight of N-methylpyrrolidone were added to form a positive electrode slurry. The positive electrode slurry was coated on an inert material, cured at 20-30°C for 46-50 hours, and then dried at 78-82°C for 11-13 hours to form a positive electrode;

[0037] The coating amount of the positive electrode slurry on the surface area of the inert material is 1.3-1.7g / 100cm 2 .

[0038] Preferably, the method comprises:

[0039] (1) After mixing 52 parts by weight of Hg2O7Sb2 and 2.5 parts by weight of platinum oxide, 32 parts by weight of N-methylpyrrolidone were added to prepare a positive electrode slurry. The positive electrode slurry was coated on an inert material, cured at 25°C for 48 hours, and then dried at 80°C for 12 hours to prepare a positive electrode;

[0040] The coating amount of the positive electrode slurry on the surface area of the inert material is 1.5g / 100cm 2 .

[0041] The third aspect of the present invention provides a use of the positive electrode as described in the first aspect of the present invention for preparing a battery.

[0042] Preferably, the battery comprises a primary battery or a secondary battery.

[0043] Preferably, the battery further comprises a negative electrode and an electrolyte.

[0044] A fourth aspect of the present invention provides a battery, comprising the positive electrode as described in the first aspect of the present invention.

[0045] Preferably, the battery comprises a primary battery or a secondary battery.

[0046] Preferably, the battery further comprises a negative electrode and an electrolyte.

[0047] Preferably, the negative electrode comprises Zn.

[0048] Preferably, the battery further comprises a separator.

[0049] Preferably, the diaphragm comprises an AGM glass fiber diaphragm.

[0050] Preferably, the thickness of the diaphragm is 0.55-1.0 mm, more preferably 0.6-1.0 mm, more preferably 0.7-0.9 mm, and most preferably 0.8 mm.

[0051] Preferably, the electrolyte comprises an aqueous solution of potassium salt.

[0052] Preferably, the electrolyte comprises an aqueous solution of potassium persulfate.

[0053] Preferably, in the potassium persulfate aqueous solution, the content of potassium persulfate is (2-4.5) g / 100 ml, preferably (3-4.5) g / 100 ml, more preferably (3.5-4.5) g / 100 ml, more preferably (3.5-4.0) g / 100 ml, for example 3.5 g / 100 ml or 4.0 g / 100 ml.

[0054] Preferably, in the potassium persulfate aqueous solution, the content of potassium persulfate is 3.0-4.0 g / 100 ml, preferably (3.2-3.7) g / 100 ml.

[0055] Preferably, in the potassium persulfate aqueous solution, the content of potassium persulfate is 3.5-4.5 g / 100 ml, preferably (3.8-4.2) g / 100 ml.

[0056] Preferably, the cut-off voltage of the battery is 0.2-1.5V, more preferably 0.2-1.2V, such as 0.3-0.5V, and most preferably 0.4V.

[0057] Preferably, the reaction mechanism of the battery positive electrode discharge includes:

[0058] Hg2O7Sb2=2HgO+2Sb+5O(10e).

[0059] Preferably, the reaction mechanism of charging the positive electrode of the battery includes:

[0060] 2HgO+2Sb+5O(10e)=Hg2O7Sb2.

[0061] Preferably, the battery charge and discharge reaction equations include:

[0062]

[0063] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (such as embodiments) can be combined with each other to form new or preferred technical solutions. DETAILED DESCRIPTION

[0064] The present invention develops a battery, wherein the positive electrode of the battery includes Hg2O7Sb2. Hg2O7Sb2 as the positive electrode active material makes the battery an oxygen-rich battery with high energy density and excellent low-voltage continuous discharge capability. It can still output high energy with a cut-off voltage as low as 0.4V. Therefore, the battery of the present invention has excellent energy density and cut-off voltage and other properties, thereby significantly improving the application value of the battery.

[0065] the term

[0066] As used herein, the terms "include," "comprising," and "including" are used interchangeably to include not only open definitions, but also semi-closed and closed definitions, including "consisting of," "consisting essentially of."

[0067] As used herein, the term "Hg2O7Sb2" refers to antimony mercury oxide.

[0068] As used herein, the term "AGM" refers to Absorbent Glass Mat.

[0069] As used herein, the term "potassium persulfate" has the chemical formula K2S2O8.

[0070] As used herein, the term "g / ml" refers to mass volume concentration. For example, in a potassium persulfate aqueous solution, a potassium persulfate content of 3.5 g / 100 ml means that 100 ml of the aqueous solution contains 3.5 g of potassium persulfate.

[0071] As used herein, the term "cut-off voltage" is also called the termination voltage, which refers to the lowest operating voltage value at which the battery is no longer suitable for further discharge when the voltage drops to a certain level during battery discharge.

[0072] positive electrode

[0073] The present invention provides a positive electrode that can be used for a battery. The positive electrode comprises a positive electrode active material, and the positive electrode active material comprises Hg2O7Sb2.

[0074] The positive electrode active material of the present invention may further contain platinum oxide.

[0075] The positive electrode active material of the present invention can be coated on the surface of an inert material. Preferably, the inert material includes an inert material sheet, an inert material rod or an inert material stick.

[0076] In a preferred embodiment of the present invention, the inert material comprises graphite. Preferably, the inert material comprises graphite sheets, graphite rods or graphite bars.

[0077] Preferably, the thickness of the inert material is 0.05-0.5 mm, more preferably 0.05-0.3 mm, more preferably 0.05-0.15 mm, and even more preferably 0.08-0.12 mm.

[0078] In a preferred embodiment of the present invention, the positive electrode comprises a positive electrode active material and an inert material, and the positive electrode active material is coated on the surface of the inert material.

[0079] In a preferred embodiment of the present invention, the Hg2O7Sb2 is 48-58 parts by weight, preferably 50-55 parts by weight, more preferably 51-53 parts by weight, and even more preferably 52 parts by weight.

[0080] In a preferred embodiment of the present invention, the platinum oxide is 0.5-8 parts by weight, preferably 1-6 parts by weight, more preferably 1-5 parts by weight, more preferably 2-3 parts by weight, and more preferably 2.5 parts by weight.

[0081] Preferably, the weight ratio of the Hg2O7Sb2 to the platinum oxide is 10-30:1, preferably 15-25:1, more preferably 18-23:1, more preferably 20-22:1, and most preferably 20.8:1.

[0082] method

[0083] The present invention also provides a method for preparing the positive electrode according to the present invention, the method comprising:

[0084] (1) Hg2O7Sb2 and platinum oxide are mixed, and a solvent is added to the mixture to form a positive electrode slurry. The positive electrode slurry is coated on an inert material, solidified, and then dried to obtain a positive electrode.

[0085] In a preferred embodiment of the present invention, the Hg2O7Sb2 is 48-58 parts by weight, preferably 50-55 parts by weight, more preferably 51-53 parts by weight, and even more preferably 52 parts by weight.

[0086] In a preferred embodiment of the present invention, the platinum oxide is 0.5-8 parts by weight, preferably 1-6 parts by weight, more preferably 1-5 parts by weight, more preferably 2-3 parts by weight, and more preferably 2.5 parts by weight.

[0087] In a preferred embodiment of the present invention, the solvent includes N-methylpyrrolidone.

[0088] Preferably, the solvent is 28-35 parts by weight, more preferably 30-34 parts by weight, and more preferably 32 parts by weight.

[0089] Preferably, the weight ratio of the Hg2O7Sb2 to the platinum oxide is 10-30:1, preferably 15-25:1, more preferably 18-23:1, more preferably 20-22:1, and most preferably 20.8:1.

[0090] Preferably, the weight ratio of the solvent to the platinum oxide is 5-25:1, more preferably 5-20:1, more preferably 10-15:1, more preferably 12-14:1, and most preferably 12.8:1.

[0091] In a preferred embodiment of the present invention, the coating amount of the positive electrode slurry on the surface area of the inert material is 0.5 g / 100 cm2 Up to 2.5g / 100cm 2 , preferably 1g / 100cm 2 Up to 2g / 100cm 2 , preferably 1.2g / 100cm 2 Up to 1.8g / 100cm 2 , preferably 1.4g / 100cm 2 Up to 1.6g / 100cm 2 , optimally 1.5g / 100cm 2 .

[0092] Typically, the method comprises:

[0093] (1) After mixing 50-54 parts by weight of Hg2O7Sb2 and 2.3-2.7 parts by weight of platinum oxide, 30-34 parts by weight of N-methylpyrrolidone were added to form a positive electrode slurry. The positive electrode slurry was coated on an inert material, cured at 20-30°C for 46-50 hours, and then dried at 78-82°C for 11-13 hours to form a positive electrode;

[0094] The coating amount of the positive electrode slurry on the surface area of the inert material is 1.3-1.7g / 100cm 2 .

[0095] Typically, the method comprises:

[0096] (1) After mixing 52 parts by weight of Hg2O7Sb2 and 2.5 parts by weight of platinum oxide, 32 parts by weight of N-methylpyrrolidone were added to prepare a positive electrode slurry. The positive electrode slurry was coated on an inert material, cured at 25°C for 48 hours, and then dried at 80°C for 12 hours to prepare a positive electrode;

[0097] The coating amount of the positive electrode slurry on the surface area of the inert material is 1.5g / 100cm 2 .

[0098] use

[0099] The present invention also provides a use of the positive electrode of the present invention for preparing a battery.

[0100] The battery of the present invention can be a primary battery or a storage battery.

[0101] Preferably, the battery further comprises a negative electrode and an electrolyte.

[0102] Battery

[0103] The present invention also provides a battery, comprising the positive electrode according to the present invention.

[0104] The battery of the present invention can be a primary battery or a storage battery.

[0105] In a preferred embodiment of the present invention, the battery further comprises a negative electrode and an electrolyte.

[0106] Preferably, the negative electrode comprises Zn.

[0107] Preferably, the battery further comprises a separator.

[0108] Preferably, the diaphragm comprises an AGM glass fiber diaphragm.

[0109] Preferably, the thickness of the diaphragm is 0.55-1.0 mm, more preferably 0.6-1.0 mm, more preferably 0.7-0.9 mm, and most preferably 0.8 mm.

[0110] In a preferred embodiment of the present invention, the electrolyte comprises an aqueous solution of potassium salt.

[0111] Preferably, the electrolyte comprises an aqueous solution of potassium persulfate.

[0112] Preferably, in the potassium persulfate aqueous solution, the content of potassium persulfate is (2-4.5) g / 100 ml, preferably (3-4.5) g / 100 ml, more preferably (3.5-4.5) g / 100 ml, more preferably (3.5-4.0) g / 100 ml, for example 3.5 g / 100 ml or 4.0 g / 100 ml.

[0113] Preferably, in the potassium persulfate aqueous solution, the content of potassium persulfate is 3.0-4.0 g / 100 ml, preferably (3.2-3.7) g / 100 ml.

[0114] Preferably, in the potassium persulfate aqueous solution, the content of potassium persulfate is 3.5-4.5 g / 100 ml, preferably (3.8-4.2) g / 100 ml.

[0115] Preferably, the cut-off voltage of the battery is 0.2-1.5V, more preferably 0.2-1.2V, such as 0.3-0.5V, and most preferably 0.4V.

[0116] The reaction mechanism of the battery positive electrode discharge of the present invention may include:

[0117] Hg2O7Sb2=2HgO+2Sb+5O(10e).

[0118] The reaction mechanism of the battery positive electrode charging of the present invention may include:

[0119] 2HgO+2Sb+5O(10e)=Hg2O7Sb2.

[0120] The battery charge and discharge reaction equations of the present invention may include:

[0121]

[0122] The main technical effects achieved by the present invention include:

[0123] 1. The present invention has developed a battery positive electrode, which includes Hg2O7Sb2. The battery prepared with Hg2O7Sb2 as the positive electrode active material is an oxygen-rich battery with high energy density and excellent low-voltage continuous discharge capability. It can still output high energy with a cut-off voltage as low as 0.4V. Therefore, the battery described in the present invention has excellent energy density and cut-off voltage, thereby significantly improving the application value of the battery.

[0124] 2. The battery of the present invention has high safety performance. After a puncture test on the battery, it will not catch fire or explode. It also has low requirements on the production environment and can be produced without special protective treatment in the production workshop.

[0125] Example 1 Battery

[0126] In this embodiment 1, a battery is prepared, and the specific method is as follows:

[0127] (1) Preparation of positive plate:

[0128] After mixing 52 parts by weight of Hg2O7Sb2 and 2.5 parts by weight of platinum oxide, 32 parts by weight of N-methylpyrrolidone were added to prepare a positive electrode slurry. The positive electrode slurry was coated on a 0.1 mm graphite sheet (the coating amount of the positive electrode slurry on the graphite surface area was 1.5 g / 100 cm 2 ), cured at 25°C for 48h, and then dried at 80°C for 12h to form a positive electrode plate.

[0129] (2) The negative electrode plate is a Zn plate.

[0130] (3) The diaphragm is AGM glass fiber diaphragm with a thickness of 0.8 mm.

[0131] (4) A separator is used to wrap the positive electrode plate and the negative electrode plate respectively, and the positive and negative electrodes are alternately formed into a battery cell. A potassium persulfate aqueous solution (wherein, the potassium persulfate content in the potassium persulfate aqueous solution is 3.5 g / 100 ml) is added to encapsulate the battery to form a storage battery.

[0132] Energy value test: Constant current discharge test is conducted using an 8-channel battery analyzer, and the discharge capacity is obtained by performing a 20h rate test in accordance with the general valve-regulated lead-acid battery part 1: technical conditions GBT19639.1-2014 standard.

[0133] The discharge capacity and power of the battery of this embodiment 1 are shown in Table 1 below:

[0134] Table 1 Battery discharge capacity and power table

[0135]

[0136]

[0137] Note: 710mWh / g is the optimal energy value of the existing ternary lithium battery positive electrode material.

[0138] As can be seen from Table 1, the battery prepared in Example 1 has excellent energy density (up to 1000 mWh / g or more) and excellent low-voltage continuous discharge capability, and can still output high energy with a cut-off voltage as low as 0.4V.

[0139] The battery of the first embodiment has high safety performance. After a puncture test on the battery sample, no fire or explosion was found.

[0140] The production environment requirements for the battery of this embodiment 1 are not high, and the production can be carried out without special protective treatment of the production workshop.

[0141] Example 2 Storage Battery

[0142] The battery of Example 2 is the same as that of Example 1, except that: Step (4):

[0143] (4) A separator is used to wrap the positive plate and the negative plate respectively, and the positive and negative plates are alternately formed into a battery unit, and a potassium persulfate aqueous solution (wherein, the potassium persulfate content in the potassium persulfate aqueous solution is 4g / 100ml) is added to encapsulate and prepare a storage battery.

[0144] The energy density of the battery prepared in Example 2 was measured to be 1462.59 mWh / g at a cut-off voltage of 0.4 V.

[0145] The battery of Example 2 has high safety performance. After a puncture test on the battery sample, no fire or explosion was found.

[0146] The production environment requirements for the battery of this embodiment 2 are not high, and the production can be carried out without special protective treatment of the production workshop.

[0147] Example 3: Battery

[0148] The battery of Example 3 is the same as that of Example 1, except that: Step (4):

[0149] (4) A separator is used to wrap the positive electrode plate and the negative electrode plate respectively, and the positive and negative electrodes are alternately formed into a battery cell, and a potassium persulfate aqueous solution (wherein, the potassium persulfate content in the potassium persulfate aqueous solution is 0.8 g / 100 ml) is added to encapsulate and prepare a storage battery.

[0150] The energy density of the battery prepared in Example 3 was measured to be 246.69 mWh / g at a cut-off voltage of 0.4 V.

[0151] The above description is merely a preferred embodiment of the present application and is not intended to limit the present application. Various modifications and variations are possible for those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. A positive electrode of a battery, characterized in that: The positive electrode of the battery comprises a positive electrode active material and an inert material, wherein the positive electrode active material is coated on the surface of the inert material; The positive electrode active material contains Hg2O7Sb2 and platinum oxide, and the weight ratio of the Hg2O7Sb2 to the platinum oxide is 10-30:1; The inert material includes graphite.

2. The positive electrode of the battery according to claim 1, characterized in that The weight ratio of the Hg2O7Sb2 to the platinum oxide is 18-23:

1.

3. The positive electrode of the battery according to claim 1, characterized in that The weight ratio of the Hg2O7Sb2 to the platinum oxide is 20-22:

1.

4. The positive electrode of the battery according to claim 1, characterized in that The weight ratio of the Hg2O7Sb2 to the platinum oxide is 20.8:

1.

5. A method for preparing the positive electrode of a battery as claimed in claim 1, characterized in that: The method includes: After Hg2O7Sb2 and platinum oxide are mixed, a solvent is added and mixed to prepare a positive electrode slurry, the positive electrode slurry is coated on an inert material, and then dried after solidification to obtain a battery positive electrode.

6. The method according to claim 5, wherein The solvent includes N-methylpyrrolidone.

7. The method according to claim 5, wherein The method includes: After mixing 50-54 parts by weight of Hg2O7Sb2 and 2.3-2.7 parts by weight of platinum oxide, 30-34 parts by weight of N-methylpyrrolidone are added to the mixture to prepare a positive electrode slurry. The positive electrode slurry is coated on an inert material, cured at 20-30°C for 46-50 hours, and then dried at 78-82°C for 11-13 hours to prepare a battery positive electrode. The coating amount of the positive electrode slurry on the surface of the inert material is 1.3-1.7g / 100cm 2 .

8. A battery, characterized in that: The battery comprises the battery positive electrode as claimed in claim 1.

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