CN102760891B - Liquid activated zinc-manganese paper battery and preparation method thereof - Google Patents
Liquid activated zinc-manganese paper battery and preparation method thereof Download PDFInfo
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Abstract
A liquid activated zinc-manganese paper battery and a preparation method thereof, zinc negative electrode, adsorbed with electrolysisFibrous paper coated with MnO and liquid 2 The pulp layer paper of the active pulp and the carbon current collector are sequentially formed in a laminated mode; according to ZnCl 2 ∶NH 4 Cl∶CaCl 2 Preparing electrolyte according to the mass ratio of 5-30: 5-50: 3-10; soaking the fiber paper in the electrolyte, and drying at 40-50 ℃ for later use; mnO is firstly added 2 Mixing the conductive agent and the additive according to the mass ratio of 80-90: 10-20: 0.1-1.0, and ball-milling to obtain MnO 2 Mixing powder; mnO of 2 The mixed powder is added with deionized water to prepare MnO 2 Active slurry is then coated on the surface of the coated paper in a scraping way and dried for later use at 40-50 ℃; sequentially superposing fiber paper adsorbed with electrolyte and coated with MnO on the surface of the zinc foil cathode 2 And the pulp layer paper of the active pulp and the carbon current collector are connected with a positive lead and a negative lead, and the plastic film is packaged in vacuum. The invention has excellent storage performance, can be stored for a long time without failure, and the voltage of the single battery can reach 1.5-1.6V.
Description
Technical Field
The invention relates to a liquid activated zinc-manganese paper battery and a preparation method thereof.
Background
The zinc-manganese battery has the advantages of low price and convenient use method, and is a battery frequently used in daily life. The paper battery is a new battery developed in recent years, which is characterized by using paper as a carrier and having flexibility and thinness, and the paper battery produced by Powerpaper company of Israel is also a battery made of zinc and MnO 2 The battery is characterized by extremely low cost, flexible appearance and size and convenient use. Enfucell Battery corporation also developed a paper battery having a composition and structure similar to those of Powerpaper corporation. Paper batteries are now beginning to be used in miniature electronic devices, especially as power sources for Radio Frequency Identification (RFID), and have a wide application prospect.
The self-discharge of the zinc-manganese battery is difficult to avoid due to the existence of liquid-phase electrolyte. The performance of the battery may be degraded and the capacity may be reduced during the storage. The inventor of the invention has conducted intensive research to drive the battery to work by using dry vacuum storage and adding liquid to activate the dry vacuum storage when the dry vacuum storage is temporarily used. Thus, the battery can be stored for a long period of time under dry vacuum conditions without deterioration. And the inventor finds that various water, body fluid, beverage and waste water can be used as an activating agent, so that the liquid activated zinc-manganese paper battery can be stored for a long time and is very convenient to use.
Disclosure of Invention
The invention aims to provide a liquid activated zinc-manganese paper battery and a preparation method thereof.
The liquid activated zinc-manganese paper battery is a laminated battery and has the structure that a zinc cathode, fiber paper absorbed with electrolyte and MnO coated 2 The laminated flexible paper battery consists of active slurry coated paper and carbon current collector.
The zinc cathode is zinc foil with the thickness of 0.1 mm-0.2 mm.
The fiber paper is quick water absorption paper or filter paper.
The electrolyte of the invention is ZnCl 2 ∶NH 4 Cl∶CaCl 2 5-30: 5-50: 3-10.
MnO of the invention 2 The active slurry is made of MnO 2 The MnO is prepared from the conductive agent and the additive according to the mass ratio of 80-90: 10-20: 0.1-1.0 2 Mixing the powder and adding MnO 2 Adding deionized water into the mixed powder to prepare MnO 2 And (3) active slurry.
MnO of the invention 2 Is electrolytic MnO 2 Active MnO of 2 MnO of fiber 2 Or nano MnO 2 One kind or two or more kinds of them.
The conductive agent is one or more than two of carbon nano tube, carbon black or superfine graphite powder.
The additive of the invention is V 2 O 5 One or more of zeolite and ZnO.
The carbon current collector is a graphite film, a carbon black film or a carbon nanotube film.
The invention relates to a liquid activated zinc-manganese paper battery and a manufacturing method thereof, wherein the manufacturing method comprises the following steps:
(1) And (4) preparing an electrolyte. According to ZnCl 2 ∶NH 4 Cl∶CaCl 2 5-30: 5-50: 3-10.
(2) And (4) treating the fiber paper. Soaking the fiber paper in the electrolyte, draining off excessive dripping liquid, and oven drying at 40-50 deg.C.
（3）MnO 2 And (3) preparing mixed powder. MnO of 2 Mixing the conductive agent and the additive according to the mass ratio of 80-90: 10-20: 0.1-1.0, and ball-milling to obtain MnO 2 And (3) mixing the powder.
（4）MnO 2 Preparation and coating of active slurry, weighing a certain amount of MnO 2 The mixed powder is added with deionized water to prepare MnO 2 Active slurry, then MnO is coated by blade coating method 2 The active slurry is coated on the surface of the coated paper by blade coating and dried for standby at 40-50 ℃.
(5) And (3) manufacturing the liquid activated zinc-manganese paper battery. Sequentially superposing fiber paper adsorbed with electrolyte on the surface of the zinc foil cathode and coating MnO 2 And simultaneously connecting the coated paper of the active slurry and the carbon current collector to form a positive lead and a negative lead, and finally carrying out vacuum packaging by using a plastic film. The structure is shown in the attached drawings.
The liquid activated zinc-manganese paper battery has the advantages that:
the storage property is excellent. Since the battery is stored under dry vacuum conditions, there is no self-discharge phenomenon, that is, the battery of the present invention can be stored for a long period of time without failure.
And (4) flexible thinning. The voltage of the single battery is 1.5-1.6V, so that the single battery can provide a low-voltage and low-current power supply for masks, plasters and the like, and the single battery is superposed and assembled into a double-body or triple-body battery, and the voltage of the single battery is 3.0-4.5V, so that the single battery can meet the requirements of various small electronic devices. For example, the dual body battery can be designed as a battery for a disposable thin handset or camera.
Excellent performance and wide application. The battery can be assembled into a low-voltage large-current or high-voltage small-current multi-body battery according to requirements, and the battery can be used for a power supply of an overhead weather detector; the liquid activator has wide source, can be various water sources, body fluids and the like, and can be stored in the mine tunnel for a long time to be used as a temporary emergency power supply or a special power supply for military communication.
The liquid activated zinc-manganese paper battery can be made into single or double paper batteries, and can be made into multi-paper batteries connected in series or in parallel according to requirements.
Drawings
The attached drawing is a cross section of the liquid activated zinc-manganese paper battery of the invention.
Wherein 1a is plastic film, 1b is plastic film, 2 is graphite sheet, 3 is MnO-coated 2 The pulp layer paper of the active pulp, the fiber paper 4 adsorbed with the electrolyte and the zinc foil 5.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1. And (3) manufacturing the liquid activated zinc-manganese paper single paper battery.
(1) Preparation of electrolyte according to ZnCl 2 ∶NH 4 Cl∶CaCl 2 Is prepared according to the mass ratio of 10: 25: 3.
(2) And (4) treating the fiber paper. Soaking filter paper in the above electrolyte for 2-3 min, draining off excessive dripping liquid, and oven drying at 40-50 deg.C for use.
（3）MnO 2 Preparation of mixed powder material by electrolysis of MnO 2 Mixing the carbon black and ZnO in a mass ratio of 9: 1:0.1, and ball-milling the mixture to prepare MnO 2 And (3) mixing the powder.
（4）MnO 2 Preparation of slurry and coating thereof, mnO 2 The mixed powder is added with deionized water to prepare MnO 2 Active slurry, then MnO is added 2 The active slurry is coated on the surface of the coated paper by blade and dried at 40-50 ℃ for standby.
(5) The liquid activated zinc-manganese paper battery is made by cutting filter paper absorbed with electrolyte into 2.2cm wide and 1.5cm thin sheet, and coating MnO 2 The coated paper, graphite film and zinc foil of the active slurry were cut into 2.0-by-1.5-cm long sheets. Sequentially superposing filter paper adsorbed with electrolyte and MnO coated on the surface of the Zn electrode 2 And assembling the coated paper of the active slurry and the graphite sheet into a four-layer battery, connecting the positive and negative leads, and finally packaging by using a plastic film vacuum sealing machine.
(6) The use method of the liquid activated zinc-manganese paper battery comprises the steps of unpacking when the battery is used, dripping 2-3 drops of tap water on the surface of the exposed dry filter paper or soaking the exposed dry filter paper in the tap water for 10-15 seconds, and then the battery can work.
Example 2. And (3) manufacturing the liquid activated zinc-manganese monomer paper battery.
(1) Preparation of electrolyte according to ZnCl 2 ∶NH 4 Cl∶CaCl 2 Is prepared according to the mass ratio of 20: 10: 5.
(2) And (4) treating the fiber paper. Soaking the quick water absorption paper in the electrolyte for 2-3 min, draining off excessive dripping liquid, and oven drying at 40-50 deg.C for use.
（3）MnO 2 Preparation of mixed powder material according to active MnO 2 V to carbon nanotubes 2 O 5 Mixing and ball-milling the materials in a mass ratio of = 9: 1 2 And (3) mixing the powder.
（4）MnO 2 Preparation of active slurry and coating thereof, mnO 2 The mixed powder is added with deionized water to be mixed and prepared into MnO 2 Active slurry, then MnO is added 2 The active slurry is coated on the surface of the coated paper by blade and dried for standby at 40-50 ℃.
(5) The liquid activated zinc-manganese paper battery is made by cutting the paper absorbed with electrolyte into 3.2cm wide 2cm thin sheet, and coating MnO 2 The coated paper of the active slurry, the carbon nanotube film and the zinc foil are cut into sheets with the length of 3cm and the width of 2 cm. Rapid water absorption paper coated with MnO and adsorbed with electrolyte sequentially superposed on surface of Zn electrode 2 The slurry paper of the active slurry and the carbon nanotube film form a four-layer battery, and the four-layer battery is connected with the leads of the anode and the cathode respectively and finally packaged by a plastic film vacuum sealing machine.
(6) When the liquid activated zinc-manganese paper battery is used, the package is disassembled, 2 to 3 drops of urine are dripped on the surface of the exposed quick absorbent paper, or the exposed quick absorbent paper is soaked in the urine for 10 to 15 seconds, and the battery can work.
Example 3. And (3) manufacturing the liquid activated zinc-manganese monomer paper battery.
(1) Preparation of electrolyte according to ZnCl 2 ∶NH 4 Cl∶CaCl 2 Is prepared according to the mass ratio of 20: 5.
(2) And (4) treating the fiber paper. Soaking filter paper in the above electrolyte for 2-3 min, draining off excessive dripping liquid, and oven drying at 40-50 deg.C for use.
（3）MnO 2 Preparation of mixed powder material according to the fibre MnO 2 Mixing the carbon nano tube and the zeolite in a mass ratio of 9: 0.5: 0.1, and ball-milling the mixture to prepare MnO 2 Mixing the powder.
（4）MnO 2 Preparation of active slurry and coating thereof, mnO 2 The mixed powder is added with deionized water to be mixed and prepared into MnO 2 Active slurry, then MnO is added 2 The active slurry is coated on the surface of the coated paper by blade and dried at 40-50 ℃ for standby.
(5) Preparation of liquid activated zinc-manganese paper batteryAs a measure, first, a dry filter paper having an electrolyte adsorbed thereon is cut into a sheet having a width of 3.2cm and a width of 2cm, and at the same time, mnO is applied 2 The coated paper of the active slurry, the carbon nanotubes and the zinc foil were cut into sheets 3cm long and 2cm wide. Sequentially superposing filter paper adsorbed with electrolyte and MnO on the surface of the Zn electrode 2 The slurry paper of the active slurry and the carbon nanotube film form a four-layer battery, and the four-layer battery is connected with the leads of the anode and the cathode respectively and finally packaged by a plastic film vacuum sealing machine.
(6) When the liquid activated zinc-manganese paper battery is used, the package is disassembled, 2 to 3 drops of purified water are dripped on the surface of the exposed dry filter paper, or the exposed dry filter paper is soaked in the purified water for 10 to 15 seconds, and the battery can work.
Example 4. And (3) manufacturing the liquid activated zinc-manganese monomer paper battery.
(1) Preparation of electrolyte according to ZnCl 2 ∶NH 4 Cl∶CaCl 2 Is prepared according to the mass ratio of 25: 3.
(2) And (3) treating the fiber paper. Soaking filter paper in the electrolyte for 2-3 min, draining off excessive dripping liquid, and oven drying at 40-50 deg.C.
（3）MnO 2 Preparation of mixed powder material according to active MnO 2 Mixing the carbon black and the ZnO in a mass ratio of 9: 0.5: 0.1, and ball-milling the mixture to prepare MnO 2 And (3) mixing the powder.
（4）MnO 2 Preparation of active slurry and coating thereof, mnO 2 The mixed powder is mixed with deionized water to prepare MnO 2 Active slurry, then MnO is added 2 The active slurry is coated on the surface of the coated paper by blade and dried for standby at 40-50 ℃.
(5) The liquid activated zinc-manganese paper battery is made by cutting filter paper absorbed with electrolyte into 3.2cm wide by 2cm thin sheet, and coating MnO 2 The coated paper, graphite film and zinc foil of the active slurry are cut into slices with the length of 3cm and the width of 2 cm. Sequentially superposing filter paper adsorbed with electrolyte and MnO on the surface of the Zn electrode 2 Active pasteThe coated paper and the graphite sheet form a battery with a four-layer structure, and the leads of the anode and the cathode are respectively connected at the same time and are finally packaged by a plastic film vacuum sealing machine.
(6) When the liquid activated zinc-manganese paper battery is used, the package is disassembled, 2 to 3 drops of cola are dripped on the surface of the dry filter paper exposed outside, or the dry filter paper exposed outside is soaked in the cola for 10 to 15 seconds, and the battery can work.
Example 5. And (3) manufacturing the liquid activated zinc-manganese monomer paper battery.
(1) Preparation of electrolyte according to ZnCl 2 ∶NH 4 Cl∶CaCl 2 Is prepared according to the mass ratio of 20: 50: 5.
(2) And (3) treating the fiber paper. Soaking the quick water absorption paper in the electrolyte for 2-3 min, draining off excessive dripping liquid, and oven drying at 40-50 deg.C for use.
（3）MnO 2 Preparation of mixed powder material according to electrolytic MnO 2 Mixing the carbon nano tube and the ZnO in a mass ratio of 9: 0.5: 0.2, and ball-milling to prepare MnO 2 Mixing the powder.
（4）MnO 2 Preparation of active slurry and coating thereof, mnO 2 The mixed powder is added with deionized water to be mixed and prepared into MnO 2 Active slurry, then MnO is added 2 The active slurry is coated on the surface of the coated paper by blade and dried at 40-50 ℃ for standby.
(5) The liquid activated zinc-manganese paper battery is made by cutting the paper with electrolyte absorbed thereon into 3.2cm wide by 2cm thin pieces, and coating MnO thereon 2 The coated paper, graphite film and zinc foil of the active slurry are cut into slices with the length of 3cm and the width of 2 cm. Rapid water absorption paper coated with MnO and adsorbed with electrolyte sequentially superposed on surface of Zn electrode 2 And the coated paper of the active slurry and the graphite sheet form a battery with a four-layer structure, and are respectively connected with the leads of the anode and the cathode, and finally are packaged by a plastic film vacuum sealing machine.
(6) When the liquid activated zinc-manganese paper battery is used, the package is disassembled, and 2 to 3 drops of rice washing water are dripped on the surface of the exposed dry quick absorbent paper, or the exposed dry quick absorbent paper is soaked in the rice washing water for 10 to 15 seconds, so that the battery can work.
Claims (1)
1. A liquid activated Zn-Mn paper battery is prepared from Zn as negative electrode, fibrous paper with adsorbed electrolyte, mnO coated paper 2 The pulp layer paper of the active pulp and the carbon current collector are sequentially formed in a laminated mode; the zinc cathode is a zinc foil with the thickness of 0.1 mm-0.2 mm, and is characterized by comprising the following steps:
(1) Preparing electrolyte: according to ZnCl 2 ∶NH 4 Cl∶CaCl 2 5-30: 5-50: 3-10;
(2) Treatment of the fiber paper: soaking the fiber paper in the electrolyte, draining off excessive dripping liquid, and oven drying at 40-50 deg.C; the fiber paper is quick water absorption paper or filter paper;
（3）MnO 2 preparing mixed powder: mnO of 2 Mixing the conductive agent and the additive according to the mass ratio of 80-90: 10-20: 0.1-1.0, and ball-milling to obtain MnO 2 Mixing the powder; the additive is V 2 O 5 One or more of zeolite and ZnO;
（4）MnO 2 preparation and coating of active slurry: weighing a certain amount of MnO 2 The mixed powder is added with deionized water to prepare MnO 2 Active slurry, then MnO is coated by blade coating method 2 Coating active slurry on the surface of coated paper, and drying at 40-50 deg.C;
(5) Manufacturing a liquid activated zinc-manganese paper battery: sequentially superposing fiber paper adsorbed with electrolyte on the surface of the zinc foil cathode and coating MnO 2 And the coated paper of the active slurry and a carbon current collector are connected with a positive lead and a negative lead at the same time, and finally vacuum-packaged by a plastic film, wherein the carbon current collector is a graphite film, a carbon black film or a carbon nanotube film.
2. The method of claim 1, wherein said MnO is formulated 2 MnO of active paste 2 Is electrolytic MnO 2 Active MnO of 2 MnO of fiber 2 Or nano MnO 2 One kind or two or more kinds of them.
3. The method of claim 1, wherein said MnO is formulated 2 The conductive agent of the active slurry is one or more than two of carbon nano tubes, carbon black or superfine graphite powder.
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| CN103824997B (en) * | 2014-03-20 | 2016-12-07 | 常州恩福赛印刷电子有限公司 | A kind of slim energy storage device and processing technology |
| CN107732067A (en) * | 2017-10-12 | 2018-02-23 | 北京军秀咨询有限公司 | Zinc-manganese battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047761A (en) * | 1989-05-30 | 1990-12-12 | 中国科学技术大学 | A kind of rigidity or flexible all-solid-state battery |
| CN101601152A (en) * | 2007-02-06 | 2009-12-09 | 恩福塞尔公司 | The method of thin battery and manufacturing thin battery |
| CN102170000A (en) * | 2011-04-02 | 2011-08-31 | 南昌大学 | Composite layer paper battery and preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047761A (en) * | 1989-05-30 | 1990-12-12 | 中国科学技术大学 | A kind of rigidity or flexible all-solid-state battery |
| CN101601152A (en) * | 2007-02-06 | 2009-12-09 | 恩福塞尔公司 | The method of thin battery and manufacturing thin battery |
| CN102170000A (en) * | 2011-04-02 | 2011-08-31 | 南昌大学 | Composite layer paper battery and preparation method |
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