WO2013044683A1

WO2013044683A1 - Method for preparing positive plate slurry of high-energy nickel/carbon super capacitor

Info

Publication number: WO2013044683A1
Application number: PCT/CN2012/079631
Authority: WO
Inventors: 周国泰
Original assignee: 天津国泰之光新材料技术研究院有限公司
Priority date: 2011-09-30
Filing date: 2012-08-03
Publication date: 2013-04-04
Also published as: CN102354615A; CN102354615B

Abstract

A method for preparing a positive plate slurry of a high-energy nickel/carbon super capacitor. The positive plate slurry comprises a positive electrode adhesive and a major material. The positive electrode adhesive accounts for 20% to 35% of the total weight of the positive electrode adhesive and the major material combined. The super capacitor comprises a positive plate made of a positive material with nickel hydroxide as major active substance, an aqueous electrolyte alkali metal hydroxide, a mixed positive plate made of a material with hydrogen storage alloy powder and an active carbon material as major active substances, and a separator sealed in a stainless steel or engineering plastic casing. The super capacitor has the characteristics such as high energy storage density and high discharge power. The super capacitor prepared by using the positive electrode material has a working voltage up to 1.3 V and a maximum energy storage density up to 65 Wh/kg, can be widely applied to power sources for electrical buses, power sources for low-temperature start of vehicles and power sources for military equipment, for example, capacitors for aircrafts and space shuttles, fighters, submarine, naval vessels and other equipment, and can also be applied to high-capacity power sources for portable equipment, for example, capacitors for notebook computers, mobile phones, and electrical tools.

Description

Method for preparing bismuth nickel carbon supercapacitor positive plate paddle

The invention belongs to the field of supercapacitors, in particular to a method for preparing a high energy nickel carbon supercapacitor positive plate slurry. Background technique

With the gradual advancement of the country's new energy construction, the research of new energy has entered a rapid development track, especially the research of supercapacitors has attracted the attention of all countries. Through the search, the following published patent documents concerning supercapacitors are found:

1. A nickel hydroxide mixed supercapacitor and a preparation method thereof (CN200810111891.2), the capacitor comprises a cylindrical type and a square structure, and comprises a nickel hydroxide anode, an alkali metal hydroxide aqueous electrolyte and activated carbon fiber The cathode seal is constructed in a stainless steel or engineering plastic casing, and has a hybrid supercapacitor with high energy storage density and high discharge power. The nickel hydroxide anode is prepared by a chemical reaction method and an electrochemical reaction method, in which an appropriate amount of carbon nanotubes and nickel carbonyl are added as an additive, and foamed nickel is used as a matrix to produce an anode. The activated carbon cathode is made of electroplated nickel-treated activated carbon fiber as a raw material, and nickel foil is used as a current collector. The assembled capacitor has an operating voltage of 1.6V, a maximum energy storage density of 20Wh/kg, and a peak discharge power of 8KW/kg. Widely used in industrial, transportation, electronics, military and other fields.

2. A vehicle start-up supercapacitor (CN03114837.9). The supercapacitor core is composed of a sintered nickel oxide positive electrode sheet enclosing a diaphragm, a continuous activated carbon fiber cloth negative electrode and a thin nickel plate supported by a current collector, and the capacitor core passes through After the current terminal is fabricated and welded, it is placed in a plastic case, and the electrolyte is injected, and the supercapacitor is obtained by sealing. The supercapacitor has high power density and energy density, and is light in weight, low in cost, long in life, and suitable for starting energy of various types of vehicles, and has good value for popularization and application.

3. A carbon-based porous electrode film for a supercapacitor and a preparation method thereof (CN200410009580.7), wherein the content of each component of the film is: an activated carbon content of 72 mass _S % to 99 mass _S %, a conductive carbon black or a graphite content of O .lmass %~20mass %, the content of zirconia nano powder is O.lmass %~5mass %, the content of nano metal nickel powder is 0.1mass%~3mass %; the void ratio is 45%~75%, further preferred void The rate is 55 % ~ 65%. Preparing the film of the invention firstly mixing the deionized water, the organic monomer and the crosslinking agent uniformly; then adding the dispersing agent to the solution and stirring uniformly to obtain a premixed solution; then adding the raw material powder, ball milling and mixing to prepare a slurry; The slurry is added with a defoaming agent and vacuum defoaming; the initiator and the catalyst are added to the defoamed slurry, stirred uniformly, and then formed, solidified and stripped on a casting machine to obtain a green body, and then subjected to a weak oxidizing atmosphere. Heat treatment to obtain a target porous electrode film. The molding process of the invention is simple, the molding time is short, the operation is easy, the film thickness is controllable, and the middle hole is developed.

4. A method for preparing a porous carbon electrode of a supercapacitor with a large rate charge and discharge performance (CN200810053475.1), The method comprises the following steps: using a microporous zeolite molecular sieve as a template, using a gas block, methane or ethylene as a carbon source, and performing vapor deposition on a quartz tube reactor by using a high-frequency heating device to obtain a microporous microporous carbon; Porous carbon

1000-160CTC high temperature heat treatment to adjust the surface properties to obtain large specific surface area porous carbon; large specific surface area porous carbon and polytetrafluoroethylene mixed and dispersed into ethanol, and prepared into a slurry, uniformly coated on the foamed nickel sheet, and then baked Dry pressing is made into a porous carbon electrode. The invention has the advantages that: the prepared large specific surface area carbon has a uniform pore structure; the porous carbon has low surface hydrophilicity and low oxygen content, and the prepared porous carbon electrode is particularly suitable for super rate charging and discharging performance super Capacitor.

5. A nickel hydroxide mixed supercapacitor and a preparation method thereof (CN200810111891.2), the capacitor comprises a cylindrical type and a square structure, and comprises a nickel hydroxide anode, an alkali metal hydroxide aqueous electrolyte and activated carbon fiber The cathode seal constitutes a hybrid supercapacitor with high energy storage density and high discharge power in a stainless steel or engineering plastic casing. The nickel hydroxide anode is prepared by a chemical reaction method and an electrochemical reaction method, in which an appropriate amount of carbon nanotubes and nickel carbonyl are added as an additive, and a foamed nickel is used as a matrix to produce an anode. The activated carbon cathode is made of electroplated nickel-treated activated carbon fiber as a raw material, and a nickel foil is used as a current collector. The assembled capacitor has an operating voltage of 1.6V, a maximum storage density of 20Wh/kg, and a peak discharge power of 8KW/kg. Widely used in industrial, transportation, electronics, military and other fields.

6. A hybrid supercapacitor and a preparation method thereof (CN200910079669.3), wherein the negative active material of the hybrid supercapacitor is one or more of a homomorphic Ή02-Β of nano-Ti02 or Ή02, positive electrode active The material is one or more of carbon nanotubes, carbon nanofibers, graphite, conductive carbon black, nickel hydroxide, manganese hydroxide or molybdenum hydroxide. The hybrid supercapacitor is made of a positive and negative electrode active material, a binder, and a conductive agent, and is assembled into an analog battery to form a supercapacitor in a glove box. The preparation method provided by the invention has the characteristics of regulation, simple preparation process and easy operation, and the assembled hybrid supercapacitor model has high specific capacity, low potential, stable performance, high current charge and discharge, long cycle life, low cost and large-scale mechanization. Production is easy to achieve and so on.

7. A method for preparing a supercapacitor (CN200910063288.6), which comprises the following steps: 1) placing a nickel foam substrate in a chemical vapor deposition reactor, introducing argon gas for 10 to 60 minutes, and exhausting the air in the furnace. Then, the temperature is raised to 450-750 ° C by heating, the hydrocarbon gas is introduced at a flow rate of 25-40 ml/min in an argon atmosphere, and the reaction is carried out at 450-75 CTC for 30 seconds to 50 minutes. After the reaction is completed, carbon nanoparticle is grown. 2) foam nickel of the tube; 2) after removing the surface loose layer product, directly use the foamed nickel substrate with carbon nanotubes grown as the supercapacitor electrode; 3) dry the two electrodes of the same thickness and size obtained in step 2, The electrolyte is fully immersed for 1-36 hours, and then separated by a separator which is also impregnated with the electrolyte to assemble a supercapacitor; the hydrocarbon gas is a block, methane, ethylene, or propylene. The carbon nanotube of the invention is directly grown on the nickel foam substrate without using an adhesive; the nickel foam is a substrate, and the electrode material has a higher bulk density and pore distribution. Reasonable.

After comparison, the positive electrode materials involved in the above patent technologies are quite different from the patent application.

Summary of the invention

SUMMARY OF THE INVENTION The object of the present invention is to overcome the deficiencies of the prior art and to provide a method for preparing a positive electrode plate slurry of a high energy nickel carbon supercapacitor having a large energy storage density and a high discharge power.

In order to solve the above technical problems, the present invention adopts the following technical solutions:

A method for preparing a high energy nickel carbon supercapacitor positive plate slurry, the steps of the preparation method are:

(1) Put the positive electrode on the mixer and mix it evenly, then put it into the batching bucket;

(2) Dissolving cobalt oxide and titania in deionized water, adding deionized water slowly, stirring while adding to avoid agglomeration of the powder to form a mixed solution;

(3) adding a mixed solution of deionized water and cobalt oxide and titanium oxide to the batching bucket, and stirring uniformly;

(4) adding high temperature additives to the batching bucket;

(5) Then add spherical nickel hydroxide, first add one-fifth, stir evenly, continue to add nickel hydroxide in batches, and put it into the mixer for stirring;

(6) Stir evenly for half an hour after the addition is completed;

(7) Thereafter, a polytetrafluoroethylene emulsion is added, and the mixture is uniformly stirred to form a positive electrode slurry.

The weight of the binder for the positive electrode is from 20% to 35% by weight based on the total weight of the positive electrode binder and the main material.

Moreover, the raw material composition of the binder for the positive electrode and the weight ratio range thereof are respectively:

Sodium carboxymethyl cellulose 2%~4%

Deionized water 96%~98%.

Moreover, the preparation method of the binder for the positive electrode is:

(1) According to the weight ratio, weigh the weight of sodium carboxymethyl cellulose and deionized water respectively;

(2) Heat the so-called deionized water to 80 ° C, pour the water into the batching tank, slowly add CMC, stir while stirring, and then place it for 24 hours to normal temperature.

Moreover, the weight percentage ranges of the respective raw materials are respectively:

Spherical nickel hydroxide 85%~95%

Cobalt oxide 0.5%~8%

Titanium oxide 0.5%~5%

High temperature additive 0.5%~5%

Polytetrafluoroethylene emulsion 2% ~ 8%. Moreover, the high temperature additive is at least one of zirconia, zinc oxide, and cerium oxide.

The advantages and positive effects of the present invention are:

1. The supercapacitor is a positive electrode plate made of a positive electrode material containing nickel hydroxide as a main active material, a mixed negative electrode plate composed of an alkali metal hydroxide aqueous electrolyte and a hydrogen storage alloy powder and an activated carbon material as main active materials, and The diaphragm seal is made of stainless steel or engineering plastic casing, which has the characteristics of high energy storage density and high discharge power.

2. The working voltage of the supercapacitor prepared by the positive electrode material of the invention reaches 1.3V, and the maximum energy storage density reaches 65Wh/kg. It can be widely used in electric power supply for electric buses, power supply for low-temperature start-up of vehicles, power supply for military equipment, capacitors for equipment such as aerospace, fighters, submarines, ships, etc. It can also be applied to high-capacity power supplies for portable equipment. Such as laptops, mobile phones, capacitors for power tools, etc. Applications include vehicles, transportation, industry, aviation, military, consumer electronics, green energy, etc., with a very broad application prospects.

Specific form

The invention will be further elucidated in the following detailed description, but the scope of the invention is not limited to the following embodiments.

The preparation method of the high-energy nickel-carbon supercapacitor positive electrode slurry of the invention is divided into two steps. The first is to prepare the adhesive for the positive electrode, which needs to be prepared one day in advance, and is prepared by mixing the positive electrode with the binder and then mixing with the main material. A positive electrode material was prepared.

Example 1

A high energy nickel carbon supercapacitor positive plate slurry prepared by:

First, the binder for the positive electrode is prepared, and the weight ratio of the raw materials is as follows:

Sodium carboxymethyl cellulose 2%

Deionized water 98%.

The steps of the preparation method are:

1. Weigh the weight of sodium carboxymethyl cellulose and deionized water, respectively;

2. Heat the deionized water to about 80 °C, pour the water into the batching bucket, slowly add sodium carboxymethylcellulose, stir while stirring, stir for 3-5 minutes, then evenly, then Leave it for 24 hours, to normal temperature, and set aside.

Second, the raw material composition and weight percentage of the main materials are as follows:

Spherical nickel hydroxide 85%

Cobalt oxide 8%

Titanium dioxide 2%

Zirconia 2%

Polytetrafluoroethylene emulsion 3%. The specific steps of the preparation method of the positive electrode plate slurry are as follows (take 100 kg as an example):

1. Put the prepared positive electrode binder on the mixer and mix it evenly into the batching barrel. The weight is 30 kg.

2. Dissolve 5.6 kg of cobalt oxide and 1.4 kg of titanium dioxide in deionized water. Note that the deionized water should be added slowly and slowly in a small amount, and stir while adding, so as to avoid agglomeration of the powder and form a mixed slurry.

3. Add the mixed slurry of deionized water and cobalt oxide and titania to the batching bucket and mix well.

4. Add high temperature additive zirconia 1.4 kg to the batching bucket.

5. Then add 59.5 kg of spherical nickel hydroxide, first add about 12 kg in a small amount, stir evenly, continue to add nickel hydroxide in 4 batches, and put it into the mixer for stirring.

6. Stir evenly for half an hour after the addition.

7. After adding PTFE (polytetrafluoroethylene) emulsion 2.1 kg, the added PTFE emulsion is a commonly used concentration, the concentration is 60%, and the solution is evenly stirred to form a positive electrode slurry.

Example 2:

A high energy nickel carbon supercapacitor positive plate slurry prepared by:

Sodium carboxymethyl cellulose 4%

Deionized water 96%.

The steps of the preparation method are:

2. Heat the so-called deionized water to about 80 °C, pour the water into the ingredient tank, slowly add sodium carboxymethyl cellulose, stir while adding, stir for a few minutes, then place 24 Hours, to normal temperature, spare.

Spherical nickel hydroxide 90%

Cobalt oxide 4%

Titanium dioxide 3%

Zinc oxide 1%

Polytetrafluoroethylene emulsion 2%.

The specific steps of the preparation method of the positive electrode plate slurry are as follows (take 100 kg as an example):

1. Prepare the adhesive for the positive electrode that has been prepared. Place it on the blender and mix it into the batching bucket. The weight is 25 kg. 2. Dissolve 3 kg of cobalt oxide and 2.25 kg of titanium dioxide in deionized water. Note that the deionized water should be added slowly and slowly in a small amount, and stir while adding, so as to avoid agglomeration of the powder and form a mixed solution.

3. Add the mixed solution of deionized water and cobalt oxide and titania to the batching bucket and mix well.

4. Add 0.75 kg of zinc oxide to the batching bucket.

5. Then add spherical silver hydroxide 67.5 kg, first add 13.5 kg in small amount, stir evenly, continue to add nickel hydroxide in 5 batches, and put it into the mixer for stirring.

6. Stir evenly for half an hour after the addition.

7. After adding 1.5 kg of PTFE (polytetrafluoroethylene) emulsion, the added PTFE emulsion is a commonly used concentration, the concentration is 60%, and the solution is stirred evenly to form a positive electrode slurry.

The test results of the high temperature and low temperature characteristics of the capacitor made from the positive electrode slurry are shown in the following table: Testing unit: Chemical Physics Power Product Quality Supervision and Inspection Center of the Ministry of Information Industry

Claims

Claim

A method for preparing a high energy nickel carbon supercapacitor positive plate slurry, characterized in that the steps of the preparation method are:

(2) Dissolving cobalt oxide and titania in deionized water, adding deionized water slowly, stirring while adding to avoid agglomeration of the powder to form a mixed slurry;

(3) adding a mixed slurry of deionized water and cobalt oxide and titanium oxide to the batching tank, and stirring uniformly;

(4) adding high temperature additives to the batching bucket;

(6) Stir evenly for half an hour after the addition is completed;

(7) after adding a polytetrafluoroethylene emulsion, stirring to form a positive electrode slurry;

2. The method for preparing a high-energy nickel-carbon supercapacitor cathode material according to claim 1, wherein: the raw material composition of the binder for the positive electrode and the weight ratio range thereof are:

Sodium carboxymethyl cellulose 2%~4%

Deionized water 96%~98%.

3. The method for preparing a high energy nickel carbon supercapacitor positive electrode slurry according to claim 2, wherein: the preparation method of the positive electrode binder is:

(2) Heat the weighed water to 80 ° C, pour the water into the batching tank, slowly add sodium carboxymethyl cellulose, stir while adding, stir well, then leave for 24 hours, until Normal temperature.

4. The method for preparing a high energy nickel carbon supercapacitor positive plate slurry according to claim 1, wherein: the weight percentage ranges of the raw materials are:

Spherical nickel hydroxide 85%~95%

Cobalt oxide 0.5%~8%

Titanium dioxide 2%~8%

High temperature additive 0.5%~5%

Polytetrafluoroethylene emulsion 2% ~ 8%.

The method for preparing a high-energy nickel-carbon supercapacitor positive electrode plate slurry according to claim 1, wherein the high-temperature additive is at least one of zirconia, zinc oxide and cerium oxide.