WO2020017351A1

WO2020017351A1 - Battery material and method of manufacturing battery

Info

Publication number: WO2020017351A1
Application number: PCT/JP2019/026764
Authority: WO
Inventors: 隆 ▲高▼澤; 博憲北嶋
Original assignee: Ｊｋ株式会社
Priority date: 2018-07-17
Filing date: 2019-07-05
Publication date: 2020-01-23
Also published as: JPWO2020017351A1

Abstract

Existing water batteries have limited life since electromotive force decreases due to the electrode material being consumed. Thus, the present invention addresses the problem of providing a battery that has a long life and a battery material for achieving the same. To solve this problem, a method of manufacturing a battery material is provided which includes: (1) a water cluster generating step of subjecting distilled water to sonication to generate water clusters; (2) a step of subjecting a graphene dispersion, which is powder graphene dispersed in the water clusters, to sonication, in order to generate a sonicated liquid, and inserting a metal electrode into the sonicated liquid and applying a voltage to generate a sonicated voltage-treated liquid; and (3) a step of mixing the graphene dispersion which is powder graphene dispersed in the water clusters and the sonicated voltage-treated liquid obtained in step (2) and applying a voltage thereto to generate a graphene-containing battery material.

Description

Battery material and battery manufacturing method

The present invention relates to a battery material and a method for manufacturing a battery.

BACKGROUND ART A water battery that generates an electromotive force by injecting water is known (for example, Patent Document 1). However, existing water batteries have a limited life because the electromotive force is reduced due to consumption of electrode materials.
Patent Document 1: JP-A-2014-203810

Issues to be solved

。 It is an object of the present invention to provide a long-life battery and a battery material for realizing the battery.

General disclosure

In order to solve the above problems, in a first aspect of the present invention, there are provided (1) a step of generating cluster water, (2) a step of generating an ultrasonic voltage treatment solution, and (3) a generation of a graphene-containing battery material. And a method of manufacturing a battery material. (1) The water generation step may be a step of performing ultrasonic treatment on distilled water to generate cluster water. (2) In the step of generating the ultrasonic voltage treatment liquid, the ultrasonic treatment is performed on the graphene dispersion liquid in which the powdered graphene is dispersed in the cluster water to generate an ultrasonic treatment liquid, and a metal electrode is inserted into the ultrasonic treatment liquid. To generate an ultrasonic voltage treatment liquid by applying a voltage. (3) In the step of generating the graphene-containing battery material, the graphene-dispersed liquid in which the powdered graphene is dispersed in the cluster water is mixed with the ultrasonic voltage treatment liquid obtained in the step (2), and a voltage is applied to the graphene-containing battery. This may be a step of producing a material.
Between step (1) and step (2), (1.1) graphite is mixed with cluster water and subjected to ultrasonic treatment while applying a voltage thereto to obtain a graphene coarse dispersion from graphite, and to obtain graphene coarse liquid. Drying the dispersion to obtain powdered graphene.
(1.1) mixing graphene powder, carbon disulfide, and cluster water between the steps (1.1) and (2), and then performing sonication to obtain a graphene suspension; (1.3) obtaining the supernatant of the graphene suspension as a graphene extract. Here, the graphene extract may be used as the graphene dispersion in step (2).
The graphene extract obtained in the step (1.3) may be used as the graphene dispersion in the step (3).
The step (4) may include a step of mixing the graphene-containing battery material obtained in the step (3), nickel oxyhydroxide, and cobalt hydroxide to obtain a battery material mixture.
In the step (4), the weight ratio of the graphene-containing battery material to the nickel oxyhydroxide in the battery material mixture may be 1:10 to 2:10.
After reacting with nickel hydroxide and hypochlorous acid aqueous solution, the supernatant liquid is removed, then, cluster water is added, ultrasonic treatment is performed, and the operation of removing the supernatant liquid is repeated. , And obtaining a dried precipitate as nickel oxyhydroxide used in step (4).
As a step (5), there is provided a method for producing a battery including a step of sandwiching a molded article containing the battery material mixture obtained in the step (4) between electrodes.
In a second aspect of the present invention, there is provided a method for producing graphene, comprising: (1) a cluster water generation step; and (1.1) a graphene generation step. (1) The cluster water generation step may be a cluster water generation step of performing ultrasonic treatment on water to generate cluster water. (1.1) In the graphene generation step, graphite is mixed with cluster water, and ultrasonic treatment is performed while applying a voltage thereto to obtain a graphene coarse dispersion from the graphite, and the graphene coarse dispersion is dried to obtain powdered graphene. To obtain graphene.
(1.1) After the step (1.2), mixing the powdered graphene, carbon disulfide, and the cluster water, and then performing sonication to obtain a graphene suspension; (1.3) graphene Obtaining the supernatant of the suspension as a graphene extract.

The summary of the invention described above does not enumerate all necessary features of the invention. Further, a sub-combination of these feature groups can also be an invention.

1 shows a first half flow illustrating a battery material and a method for manufacturing a battery in the present embodiment. 2 shows a second half flow illustrating a battery material and a method for manufacturing a battery according to the present embodiment. An example of a (1.1) graphene coarse dispersion generation step in the present embodiment is shown. An example of a change in volume of the graphene coarse dispersion at the stage (1.1) is shown. It is a photograph of the graphene suspension before the process of (1.2) stage. It is a photograph of the graphene suspension after the process of (1.2) stage. It is a photograph of the ultrasonic voltage processing liquid obtained in (2) stage. A photograph of the graphene-containing battery material obtained in step (3) is shown. 4 shows a scanning electron micrograph of the battery material mixture obtained in step (4). FIG. 9A is an enlarged view of a part of FIG. 9A. 1 shows an example of a battery using the battery material according to the present embodiment. 4 shows a photograph of an example of a battery using the battery material in the example. 4 shows output characteristics of a battery using a battery material in Examples. 4 shows output aging characteristics of a battery using a battery material in an example. 13 shows an example of a production example of a battery according to Example 7. 13 shows an example of a production example of a battery according to Example 7. 13 shows an example of a production example of a battery according to Example 7. 13 shows an example of a production example of a battery according to Example 7. 13 shows an example of a production example of a battery according to Example 7. An example of an expected electromotive reaction is shown.

Hereinafter, the present invention will be described through embodiments of the present invention. The following embodiments do not limit the invention according to the claims. In addition, not all combinations of the features described in the embodiments are necessarily essential to the solution of the invention. In the following embodiments, unless otherwise specified, operations, measurements, and the like may be performed at room temperature and a relative humidity of 40% RH or more and 60% RH or less, and / or normal pressure (for example, 1 atm). The room temperature may be, for example, 20 to 25 ° C. (for example, 25 ° C.).

First, the battery material and the method for manufacturing the battery according to the present embodiment will be described. The battery material according to the present embodiment may be used as a battery material for various batteries including a water battery. For example, the battery material may be used as an active material or a catalyst for a water battery.

[Description of Battery Material and Battery Manufacturing Method]
FIG. 1 shows a first half flow showing a battery material and a method for manufacturing a battery in this embodiment, and FIG. 2 shows a second half flow. The battery according to the present embodiment may be manufactured by performing at least a part of the steps (1) to (5) shown in FIGS.

(1) Cluster water generation step First, in step (1), cluster water is generated. In the present specification, the cluster water may be water that has been subjected to any crushing treatment. For example, cluster water may be generated by performing ultrasonic treatment on water having no or little impurities such as distilled water, pure water, or ultrapure water.

The ultrasonic treatment may be performed by an ultrasonic irradiator such as an ultrasonic homogenizer. Also, the sonication may be performed for 10 to 180 minutes, preferably 30 to 90 minutes.

(1.1) Powder Graphene Generation Step Next, in the step (1.1), powder graphene is generated. For example, first, graphite is mixed with the cluster water generated in the step (1), and ultrasonic treatment is performed while applying a voltage thereto to obtain a graphene coarse dispersion from graphite. Further, the graphene coarse dispersion may be dried to obtain powdered graphene.

For example, to produce a graphene coarse dispersion, graphite and cluster water are mixed and stirred to obtain a graphite suspension, two electrodes are inserted into the suspension, and a DC voltage is applied by a voltmeter while the graphite suspension is superimposed. The sonication may be performed simultaneously. Here, commercially available graphite may be used. A commercially available electrode may be used as the electrode. For example, a wire mesh such as stainless steel that does not react with graphite may be used as the electrode. By the above processing, an electric field (electric field) is generated in the beaker. When the graphene separated by the ultrasonic treatment passes through this electric field, -electrons are charged on the layer surface, and an "electrostatic repulsion effect" occurs between the graphene layers. It is determined that re-aggregation does not occur due to this effect. However, when a high voltage is applied, the graphite itself separates and is divided into a beaker bottom and an upper layer. In particular, "dama" is generated in the upper layer, and it becomes impossible to affinity with pure water. The ultrasonic treatment may be performed by an ultrasonic irradiator such as an ultrasonic homogenizer.

FIG. 3 shows an example of the step (1.1) of generating a coarse graphene dispersion in the present embodiment. As shown, the graphene coarse dispersion generation step is performed in the soundproof box 310. A graphite suspension 303 in which graphite and cluster water are mixed is stored in a container such as a beaker. Here, the electrode 304 and the electrode 306 are inserted, and a DC voltage is applied to the graphite suspension 303 from the voltage generator 307 via the electrode 304 and the electrode 306. Further, the ultrasonic oscillator of the ultrasonic homogenizer 308 is also inserted here. The voltage of the DC current is preferably, for example, 1 to 60 V, and is preferably performed for 10 to 180 minutes. Thereby, the ultrasonic treatment and the voltage application are performed simultaneously.

(4) As a result, the exfoliation of the graphite layer structure proceeds, and a coarse graphene dispersion liquid 302 is generated in the lower phase of the graphite suspension 303. As the processing time elapses, the amount of the generated graphene coarse dispersion 302 increases, but the generated amount is saturated in a certain time.

FIG. 4 shows an example of a change in volume of the coarse graphene dispersion at the stage (1.1). The vertical axis in FIG. 4 shows the volume (ml) of the generated graphene coarse dispersion 302, and the horizontal axis shows the elapsed time of the ultrasonic / voltage application processing. As shown in the figure, the generation amount of the graphene coarse dispersion 302 increases from the start of the treatment, but the generation amount is saturated after 20 minutes. Therefore, the ultrasonic treatment is preferably performed within 30 minutes, preferably within about 20 minutes. In addition, when the processing time is short, a part of the graphene may aggregate and return to graphite. Therefore, the ultrasonic treatment is preferably performed for 5 minutes or more, preferably about 10 minutes or more.

Thereafter, the lower phase graphene coarse dispersion is separated from the graphite suspension, and the separated graphene coarse dispersion is dried to obtain powdered graphene. Drying of the graphene coarse dispersion may be performed by various drying means. For example, a vacuum rotary evaporator may be used as the drying means.

According to the present embodiment, by performing the step (1.1), powder graphene is generated without using a high-cost and low-efficiency conventional manufacturing method such as a SiC thermal decomposition method or a chemical vapor deposition method (CVD method). be able to. In the modification of this embodiment, instead of the graphene generated in the step (1.1), graphene generated by a conventional manufacturing method, commercially available graphene, or the like may be used in a subsequent step.

(1.2) Graphene suspension generation step Next, the graphene powder generated in the step (1.1), carbon disulfide, and the cluster water generated in the step (1) are mixed. For example, 0.5 to 2 g of powdered graphene and 10 to 100 ml of carbon disulfide are mixed with 100 ml of cluster water. Thereafter, the mixture is subjected to ultrasonic treatment to obtain a graphene suspension. For example, ultrasonic treatment is performed for 10 minutes to 3 hours using an ultrasonic cleaner or an ultrasonic homogenizer.

により Thereby, graphene is dispersed in the cluster water in the graphene suspension. In addition, contamination components such as oil contained in graphene are washed with carbon disulfide, and the purity of graphene is improved. The graphene suspension separates into two phases: a cluster water / graphene phase on the supernatant side and a carbon disulfide phase on the lower side.

FIG. 5 is a photograph of the graphene suspension before the ultrasonic treatment in the step (1.2). As illustrated, cluster water 501, graphene 502, and carbon disulfide 503 are separated into layers.

FIG. 6 is a photograph of the graphene suspension after the treatment in step (1.2). As shown, the graphene suspension is separated into a cluster water / graphene phase 601 and carbon disulfide 602.

(1.3) Graphene Dispersion Liquid Producing Step Next, the supernatant (ie, cluster water / graphene phase) of the graphene suspension generated in step (1.2) is obtained as a graphene extract. The supernatant may be extracted from the graphene suspension using a known technique such as a dropper, a gradient method, and centrifugation.

As described above, in this embodiment, by performing (1.1) to (1.3), a graphene dispersion liquid in which graphene is dispersed in water can be generated. That is, (1.1) to (1.3) can be regarded as a method for producing graphene (and a graphene dispersion). According to the method for manufacturing graphene (graphene dispersion liquid) of the present embodiment, an electrostatic repulsion effect is generated between the graphenes by the electric treatment, and the aggregation of graphene can be prevented. As a result, graphene with improved dispersibility can be obtained. As a result, according to the manufacturing method of the present embodiment, the resistance value of graphene can be reduced, and the conductivity can be improved. In this embodiment, steps (1.2) to (1.3) are mainly performed to remove contaminants. However, when the method is used as a method for producing graphene, steps (1.2) to (1.3) May be omitted and only (1.1) may be performed.

In the following, the manufactured graphene is further processed to obtain a graphene-containing battery material, but the graphene manufactured in the present embodiment may be used for other known applications. For example, it may be used for a conductive material, a reinforcing material, or a paint, an ink, or other additives.

(2) Ultrasonic voltage treatment liquid generation step Next, ultrasonic treatment is performed on the graphene dispersion liquid in which powdered graphene is dispersed in cluster water to generate an ultrasonic treatment liquid, and a metal electrode is inserted into the ultrasonic treatment liquid. A voltage is applied to generate an ultrasonic voltage treatment liquid. For example, the graphene extract obtained in step (1.3) may be used as a graphene dispersion.

As an example of this, a graphene extract obtained by diluting the graphene extract obtained in step (1.3) with the cluster water obtained in step (1) may be used as a graphene dispersion. As an example, the graphene extract obtained in step (1.3) and the cluster water generated in step (1) may be diluted at a ratio of 1: 4 to 1: 6. The dilution can promote the reaction in step (3) described below.

As another example of this, the graphene extract itself obtained in the step (1.3) may be used as a graphene dispersion. In yet another embodiment, a commercially available graphene dispersed in distilled water, pure water, ultrapure water, or the like may be used as the graphene dispersion.

超 The ultrasonic treatment and the voltage application in the stage (2) may be performed by the same device configuration as that described in FIG. 3 in the paragraph (1.1). However, in the step (2), the ultrasonic treatment and the voltage application are not performed simultaneously but individually. For example, in step (2) of the present embodiment, the graphene extract is first subjected to ultrasonic treatment to generate an ultrasonic treatment liquid. The ultrasonic treatment is desirably performed for 10 to 60 minutes using an ultrasonic homogenizer or the like. Thereafter, a voltage is applied to the ultrasonic treatment liquid to generate an ultrasonic voltage treatment liquid.

In voltage application, the same electrodes as those used in the paragraph (1.1) may be used. However, at least one of the positive and negative electrodes is preferably made of a nickel-based material. The voltage is preferably applied by direct current, and it is desirable to apply a higher voltage (for example, 24 to 60 V) and / or a longer time (for example, 20 to 30 hours) than in the step (1.1). Thereby, the metal electrode material and the graphene can be promoted.

処理 By this treatment, metal ions such as nickel ions are probably eluted from the electrode and aggregate in the process of moving to the cathode. At that time, it is presumed that carbon fine particles such as graphene in water adhere and a transition metal complex (metal oxide semiconductor bonded to carbon molecules) precipitates.

FIG. 7 is a photograph of the ultrasonic voltage treatment solution obtained in step (2). As shown in FIG. 7, a yellow and transparent ultrasonic voltage treatment liquid is obtained by the treatment of the step (2).

(3) Battery material generation step Next, a graphene dispersion liquid in which powdered graphene is dispersed in cluster water is mixed with the ultrasonic voltage treatment liquid obtained in step (2), and a voltage is applied to generate a graphene-containing battery material. I do. For example, the graphene extract itself obtained in step (1.3) or the graphene extract diluted with cluster water may be used as the graphene dispersion. Alternatively, a commercially available graphene dispersed in distilled water, pure water, ultrapure water, or the like may be used as the graphene dispersion liquid.

For example, the graphene dispersion liquid: the ultrasonic voltage treatment liquid may be mixed at a ratio of 10: 1 to 1:10. An electrode pair may be inserted into a mixture of the graphene dispersion liquid and the ultrasonic voltage treatment liquid, and a voltage may be applied. The voltage is desirably a DC voltage of 12 to 60V. An electrode that does not react with the mixed solution such as a stainless steel wire mesh may be used as the electrode. Further, the voltage application time is desirably 1 to 5 hours. It is presumed that a carbon compound in which a transition metal complex is supported on the surface of carbon particles such as graphene is obtained by the treatment in the step (3).

FIG. 8 shows a photograph of the graphene-containing battery material obtained in step (3). As illustrated, the substance presumed to be the transition metal complex 802 appears white in the graphene-containing battery material 800.

(4) Battery Material Mix Generation Step Next, the graphene-containing battery material obtained in the step (3), nickel oxyhydroxide, and cobalt hydroxide are mixed to obtain a battery material mixture. The battery material mixture may be pressure molded after mixing. The mixing ratio may be an arbitrary ratio. For example, the weight ratio of the graphene-containing battery material to the nickel oxyhydroxide in the battery material mixture is 0.1: 10 to 10:10, preferably 1:10 to It may be 2:10. The graphene-containing battery material may be mixed with any material other than nickel oxyhydroxide and cobalt hydroxide.

コバルト Cobalt hydroxide may be added for the purpose of improving the conductivity of the battery material mixture. For example, the weight ratio of cobalt hydroxide to nickel oxyhydroxide in the battery material mixture may be from 0.01: 10 to 2:10, preferably from 0.1: 10 to 1:10.

Here, as the nickel oxyhydroxide, a commercially available product may be used, or a product synthesized in-house may be used. In the case of synthesizing, after reacting with nickel hydroxide and aqueous hypochlorous acid, the supernatant liquid is removed, then, cluster water is added, ultrasonic treatment is performed, and one or more operations for removing the supernatant liquid are performed. Repeating the steps, drying the finally precipitated precipitate may be performed, and the dried precipitate may be obtained as nickel oxyhydroxide used in step (4).

The sonication may be performed by an ultrasonic homogenizer for 1 minute to 1 hour. For example, nickel oxyhydroxide NiOOH is obtained by the following reaction.
Ni (OH) ₂ + 2HClO → NiOOH + 2HCl + O ₂ {+ H}

FIG. 9A shows a scanning electron micrograph of the battery material mixture obtained in step (4). FIG. 9B shows an enlarged part of FIG. 9A. As shown in the figure, spherical nickel oxyhydroxide 902 and transition metal complex 904 of plate or amorphous graphene-containing battery material are observed in the battery material mixture.

(5) Battery Manufacturing Step Next, a battery is manufactured by sandwiching the molded body containing the battery material mixture obtained in the step (4) between electrodes. For example, the battery material mixture may be molded and cured with a binder resin or the like and / or molded under pressure to form a battery material solid, which may be sandwiched between electrodes. Here, the solid material of the battery may include an amount of a water absorbing material such as a nonwoven fabric or parator paper so that the solid material of the battery can come into contact with moisture when water is given.

FIG. 10 shows an example of a battery using the battery material according to the present embodiment. The battery according to FIG. 10 includes a battery material mixture 1002, a positive electrode 1004, a negative electrode 1006, water 1010, and a load 1012.

As shown, the battery material mixture 1002 is sandwiched between the positive electrode 1004 and the negative electrode 1006, and the assembly of the battery material mixture 1002, the positive electrode 1004, and the negative electrode 1006 is immersed in water 1010. Accordingly, the battery generates an electromotive force, and operates the load 1012 such as a light bulb connected to the positive electrode 1004 and the negative electrode 1006 by wiring. For example, the positive electrode 1004 may be a copper plate and the negative electrode 1006 may be an aluminum plate. Although only one set of assemblies is shown in FIG. 10, a plurality of assemblies may be stacked and connected in parallel or in series.

[Example]
Hereinafter, examples in which the battery material and the like of the present embodiment are manufactured will be described.

[Battery material production example 1]
(1) Generation of Cluster Water 500 ml of distilled water was put into a beaker, and subjected to ultrasonic treatment using an ultrasonic homogenizer (Q700 manufactured by QSONICA, microchip 4220 specification) for 30 minutes. Thereby, cluster water A was generated.

(1.1) Production of powdered graphene 15 g of artificial graphite was put into 500 ml of cluster water A, followed by stirring to obtain a graphite suspension B. Ultrasonic application and voltage application were simultaneously performed on the graphite suspension B by the apparatus configuration described with reference to FIG. Here, a DC voltage was applied to the graphite suspension B for 30 minutes using a stainless steel wire mesh (JIS SUS430) as an electrode. An ultrasonic homogenizer (QSONICA Q700, microchip 4220 specification) was used for ultrasonic application.

(4) As a result, approximately 100 ml of the graphene coarse dispersion C was phase-separated into the lower phase of the graphite suspension B. Thereafter, only the graphene coarse dispersion C was extracted from the graphite suspension B. The graphene coarse dispersion C was charged into a vacuum rotary evaporator and dried under vacuum to obtain powdered graphene D.

(1.2) Formation of graphene suspension 100 ml of cluster water A, 0.5 g of powdered graphene D, and 50 ml of commercially available carbon disulfide were mixed. The mixed solution was subjected to an ultrasonic treatment for 1 hour by an ultrasonic cleaner (US-1KS, AS-ONE) to separate the cluster water / graphene phase (upper phase) and carbon disulfide (lower phase) into graphene suspension. A suspension E was obtained.

(1.3) Formation of Graphene Dispersion Liquid The upper phase portion of the graphene suspension E was obtained with a dropper or the like and used as a graphene extract F.

(2) Generation of ultrasonic voltage treatment liquid Cluster water A and graphene extract F were mixed at a volume ratio of 1: 5, and the graphene dispersion G was mixed with an ultrasonic homogenizer (QSONICA Q700, microchip 4220 specification). Ultrasonic application was performed for 10 minutes to produce an ultrasonic treatment liquid H.

After the application of ultrasonic waves, a nickel electrode pair or a nickel-plated electrode pair was inserted into the ultrasonic treatment liquid H, and a voltage was applied at DC 24 V for 20 hours to produce an ultrasonic voltage treatment liquid I.

(3) Production of battery material 350 ml of graphene extract F and 150 ml of ultrasonic voltage treatment solution I were mixed and stirred. Further, a stainless steel wire mesh electrode pair was inserted into the mixed solution, and a voltage was applied at DC 24 V for 2 hours to obtain a graphene-containing battery material J.

[Battery material production example 2]
A graphene-containing battery material J was produced in the same manner as in Battery Material Production Example 1 except that the following conditions were changed.
(1) In the generation of cluster water, ultrasonic treatment was performed for 60 minutes.
(1.1) In producing graphene powder, a direct current was applied for 20 minutes using a stainless steel wire mesh (JIS standard SUS304).
(1.2) In producing graphene suspension, 1.0 g of graphene powder D was used.
(2) In the generation of the ultrasonic voltage treatment solution, the voltage was applied at 24 V for 20 hours.
(3) In producing the battery material, a direct current of 24 V was applied for 2 hours.

(4) Battery manufacture [Example 1]
The materials were mixed at the following composition ratio, and a molded article (dimensions: 20 mm × 40 mm × 0.5 mm) obtained by pressure molding was obtained.
Graphene-containing battery material J produced in Battery Material Production Example 1: 3 parts by weight,
Nickel oxyhydroxide: 6.9 parts by weight,
Cobalt hydroxide: 0.1 parts by weight

(4) The molded product was sandwiched between a positive electrode of a copper plate (dimensions: 20 mm × 40 mm × 0.1 mm) and a negative electrode of an aluminum plate (dimensions: 20 mm × 40 mm × 0.1 mm) to form an assembly. Wiring was connected to the positive and negative electrodes of the assembly and immersed in water. Thus, a water battery was obtained.

[Example 2]
A water battery was manufactured in the same procedure as in Example 1.

[Example 3]
A water battery was manufactured in the same manner as in Example 1 except that the composition ratio was changed as follows.
Graphene-containing battery material J: 4 parts by weight,
Nickel oxyhydroxide: 5.9 parts by weight,
Cobalt hydroxide: 0.1 parts by weight

[Example 4]
A water battery was manufactured in the same procedure as in Example 3.
[Example 5]
A water battery was manufactured in the same manner as in Example 1 except that the composition ratio was changed as follows.
Graphene-containing battery material J: 5 parts by weight,
Nickel oxyhydroxide: 4.9 parts by weight,
Cobalt hydroxide: 0.1 parts by weight

[Example 6]
A water battery was manufactured in the same procedure as in Example 5.

FIG. 11 shows photographs of an example of the batteries manufactured in Examples 1 to 6.

FIG. 12 shows the output characteristics of the batteries using the battery materials in Examples 1 to 6. As shown, the batteries manufactured in Examples 1 to 6 exhibited good voltage characteristics, current characteristics, and power characteristics.

FIG. 13 shows the output aging characteristics of the battery using the battery material in Example 1. As shown, the battery according to Example 1 still maintains current and voltage for more than 100 days, indicating that it has a very long life.

[Example 7]
A mixture of 2.0 g of the graphene-containing battery material J manufactured in Battery Material Manufacturing Example 1 and 11.0 g of nickel oxyhydroxide was divided into six equal portions, each of which was charged into six test tubes, and further pure water was injected. did. When a copper electrode and an aluminum electrode were inserted into the settled mixture, and these electrodes were connected to the LED via wiring, the LED was turned on.

～ FIGS. 14 and 15 show photographs of a production example of the battery according to the seventh embodiment. In Example 7, two types of six-cell batteries were prepared by using two types of artificial graphites having different particle sizes for the artificial graphite (used in the (1.1) powder graphene generation step) as a raw material of the graphene-containing battery material J. Was manufactured. Specifically, one uses artificial graphite A having a small particle size (manufactured by Ito Graphite Industry Co., Ltd., trade name: Z-5F, fixed carbon content: 99.11%, particle size: 4.38 μm), and the other uses Artificial graphite B having a large particle size (trade name 075-01325, manufactured by Wako Pure Chemical Industries, Ltd.) was used. The battery using artificial graphite A had an average output of 3.4 V (0.56 V per cell), and the battery using artificial graphite B had an average output of 3.2 V (0.53 V per cell). The same voltage was confirmed, but the current value was better for the type using artificial graphite A having a small particle size.

[Example 8]
2.0 g of the graphene-containing battery material J produced in Battery Material Production Example 1 and 11.0 g of nickel oxyhydroxide were mixed with 2.0 g of a water-soluble binder (SBR binder: TRD102A) to form a paint. This was applied to both sides of a nonwoven fabric (SP-1070E-HY), dried, and then subjected to a lamination treatment by sandwiching it between a copper electrode and an aluminum electrode to obtain a battery material resin composite. Pure water was absorbed by the battery material-resin composite, connected to the LED via wiring, and the LED was turned on. The specifications of the LED were as follows: voltage: 2.0 V, current value: 50 mA. 16, 17A, and 17B show photographs of a manufacturing example of the battery according to Example 8.

Next, an electromotive mechanism by the battery material of the present embodiment will be outlined. (3) The transition metal complex (for example, the transition metal complex 802 shown in FIG. 8 and the transition metal complex 1804 shown in FIG. 18) in the graphene-containing battery material obtained by forming the battery material reacts with H ₂ O to generate hydrogen. Occurs. Nickel oxyhydroxide (NiOOH: nickel oxyhydroxide 1802 in FIG. 18) reacts with the generated hydrogen to be oxidized to nickel hydroxide Ni (OH) ₂ , at which stage electrons are emitted. On the other hand, when the positive electrode and the negative electrode are connected to an external circuit, electricity flows, and is returned to nickel oxyhydroxide again by the reduction action of the catalytic reaction of the transition metal complex. Note that since nickel oxyhydroxide is an insulator, a small amount of cobalt hydroxide is added to make it conductive and help transfer of emitted electrons. From the above, it can be assumed that the graphene-containing battery material acts as a “graphene catalyst”. The reaction is as follows.
Also, H ₂ O is required as a solvent. Pure water is optimal, but if it is an aqueous solution, electromotive force is possible. The experiment requires a few drops per day per test tube, including the evaporation of H ₂ O.
^{(1) NiOOH + H + +} e - → Ni (OH) 2 oxidation reaction _{(2) Ni (OH) 2} + OH - → NiOOH + H 2 O + e - reduction reaction

It is presumed that electrons move by connecting an external circuit, and the oxidation-reduction reaction is repeated. In the case of power generation using a potential difference between copper and aluminum, when a circuit is connected, an electrolytic corrosion reaction of aluminum, which changes to aluminum oxide, usually occurs. In this catalytic power generation, although H ₂ O was used as a solvent, there was a possibility that a slight electrolytic corrosion reaction might occur, but almost no dissolution of aluminum was confirmed.

Nickel oxyhydroxide (NiOOH) is generally used as a positive electrode material of a “nickel-metal hydride battery”. The oxidation-reduction reaction is repeated by charging and discharging, and the voltage generated from the reaction is as follows. (Https://en.wikipedia.org/wiki/Nickel(II) hydroxide)
NiOOH + H ₂ O + e ⁻ ⇔Ni (OH) ₂ + OH ⁻ , E (electromotive voltage) = 0.48 V

As described above, in Example 7, a voltage of 0.53 to 0.56 V was generated per battery, and it is estimated that a voltage was substantially generated by the oxidation-reduction reaction of nickel oxyhydroxide (NiOOH). it can. It can be presumed that the voltage is slightly positive and that the voltage is related to the potential difference due to the difference in ionization tendency between the two electrodes. In addition, the difference between the results of Example 7 using the artificial graphite A and the types using the artificial graphite B may be caused by the difference in the graphite (graphite) as a starting material when producing graphene. It is generally known that the higher the solid carbon component and the smaller the particle size, the higher the conductivity. As a result, it is possible that the use of artificial graphite B resulted in a better current value.

FIG. 18 shows an example of an expected electromotive reaction. As shown in FIG. 18, the reaction is considered to have occurred at the interface 1803 between the nickel oxyhydroxide 1802 and the graphene-containing battery material 1804. The graphene-containing battery material 1804 has a square shape, and the nickel oxyhydroxide 1802 has a spherical shape. When pure water is charged, nickel oxyhydroxide 1802 is first oxidized to nickel hydroxide. At this time, electromotive force is started. The voltage at this point measures an output of about 1.0 V, but drops after several hours. The nickel oxyhydroxide 1802 becomes nickel hydroxide and is stabilized. (It becomes an insulator). Since the graphene-containing battery material 1804 has a catalytic reaction, the “redox reaction” is repeated only at the interface 1803 with nickel oxyhydroxide. The output at this time is 0.48V.

The present invention has been described using the embodiments. The technical scope of the present invention is not limited to the scope described in the above embodiment. It is apparent to those skilled in the art that various changes or improvements can be made to the above embodiment. It is apparent from the description of the appended claims that embodiments with such changes or improvements can be included in the technical scope of the present invention.

The execution order of each processing such as operation, procedure, step, and stage in the processes and methods shown in the claims, the description, and the drawings is specifically indicated as "before", "before", and the like. It should be noted that they can be implemented in any order as long as the output of the previous process is not used in the subsequent process. Even if the operation flow in the claims, the specification, and the drawings is described using “first”, “next”, etc. for convenience, it means that it is essential to implement in this order is not.

302 Rough dispersion of graphene 303 Graphite suspension 304 Electrode 306 Electrode 307 Voltage generator 308 Ultrasonic homogenizer 310 Soundproof box 501 Cluster water 502 Graphene 503 Carbon disulfide 601 Cluster water / graphene phase 602 Carbon disulfide 800 Graphene-containing battery material 802 Transition Metal complex 902 Nickel oxyhydroxide 904 Transition metal complex 1002 Battery material mixture 1004 Positive electrode 1006 Negative electrode 1010 Water 1012 Load 1802 Nickel oxyhydroxide 1803 Interface 1804 Graphene-containing battery material

Claims

(1) a cluster water generation step of performing ultrasonic treatment on water to generate cluster water;
(2) Ultrasonic treatment is performed on a graphene dispersion liquid in which powdered graphene is dispersed in cluster water to generate an ultrasonic treatment liquid, and a metal electrode is inserted into the ultrasonic treatment liquid to apply a voltage to apply an ultrasonic voltage treatment liquid. Stages and
(3) mixing a graphene dispersion liquid in which powdered graphene is dispersed in cluster water with the ultrasonic voltage treatment liquid obtained in step (2), applying a voltage, and generating a graphene-containing battery material;
A method for producing a battery material comprising:
Between the steps (1) and (2),
(1.1) Graphite is mixed with the cluster water and subjected to ultrasonic treatment while applying a voltage thereto to obtain a graphene coarse dispersion from the graphite, and the graphene coarse dispersion is dried to obtain powder graphene. A graphene generation stage;
The method for producing a battery material according to claim 1, comprising:
Between the steps (1.1) and (2),
(1.2) mixing the powdered graphene, carbon disulfide, and the cluster water, and then performing ultrasonic treatment to obtain a graphene suspension;
(1.3) obtaining a supernatant of the graphene suspension as a graphene extract;
With
Using the graphene extract as the graphene dispersion in step (2);
A method for producing the battery material according to claim 2.
The method for producing a battery material according to claim 3, wherein the graphene extract obtained in the step (1.3) is used as the graphene dispersion in the step (3).
(4) a step of mixing the graphene-containing battery material obtained in the step (3), nickel oxyhydroxide, and cobalt hydroxide to obtain a battery material mixture;
A method for producing the battery material according to claim 1.
In the step (4), the weight ratio of the graphene-containing battery material to the nickel oxyhydroxide in the battery material mixture is 1:10 to 2:10.
A method for producing the battery material according to claim 5.
After reacting with nickel hydroxide and aqueous hypochlorous acid, remove the supernatant,
Thereafter, the above-mentioned cluster water was added, ultrasonic treatment was performed, and the operation of removing the supernatant was repeated,
Finally, a step of drying the precipitated precipitate is performed,
Obtaining the dried precipitate as the nickel oxyhydroxide used in step (4).
A method for producing a battery material according to claim 5.
(5) A method for producing a battery, comprising a step of sandwiching a molded article containing the battery material mixture obtained in the step (4) according to the step (4) between electrodes.
(1) a cluster water generation step of performing ultrasonic treatment on water to generate cluster water;
(1.1) Graphite is mixed with the cluster water and subjected to ultrasonic treatment while applying a voltage thereto to obtain a graphene coarse dispersion from the graphite, and the graphene coarse dispersion is dried to obtain powder graphene. A graphene generation stage;
A method for producing graphene, comprising:
After the step (1.1),
(1.2) mixing the powdered graphene, carbon disulfide, and the cluster water, and then performing ultrasonic treatment to obtain a graphene suspension;
(1.3) obtaining a supernatant of the graphene suspension as a graphene extract;
The method for producing graphene according to claim 9, further comprising: