RU2522947C2 - Supercapacitor with inorganic composite electrolyte (versions) - Google Patents

Abstract

FIELD: electricity.

SUBSTANCE: supercapacitor is made of composite containing nano-sized LiMn_2-xMe_xO₄ oxide where Me=Ni²⁺, Mn³⁺, and solid composite electrolyte and conductive black for symmetrical version of supercapacitor. For asymmetrical version of supercapacitor, negative electrode is made of nano-sized manganese oxide MnO₂ and separated by solid electrolyte based on lithium perchlorinate 0.4LiClO₄ - 0.6Al₂O₃. In addition, supercapacitor includes current feed line made out of two metal nickel plates attached to external sides of electrodes.

EFFECT: improved specific electric capacitance of supercapacitor in a wide temperature range.

2 cl, 1 dwg

Description

The invention relates to the field of solid-state micro- and nanoelectronics, in particular to supercapacitors with inorganic composite solid electrolyte, which can be used in various hybrid devices as a power source, due to the electric charge accumulated in them.

Solid-state supercapacitors are known in which proton-conducting polymer electrolytes are used [1. Keryn Lian, Qifeng Tian Electrochemistry Communications 12 (2010) 517-519 Solid asymmetric electrochemical capacitors using proton-conducting polymer electrolytes] [Han Gao, Keryn Lian, High rate all-solid electrochemical capacitors using proton conducting polymer electrolytes Journal of Power Sources 196 ( 2011) 8855-8857]. The disadvantage of these supercapacitors is the presence of acids that impregnate polymer membranes, which leads to the need to search for corrosion-resistant materials for the manufacture of an electrochemical cell. Also, due to the fact that they contain toxic organic compounds, problems arise in the disposal of spent electrochemical cells.

Currently known supercapacitors are unstable to temperature effects due to thermal decomposition of the electrolyte with possible fire.

The disadvantages of the known, to the present moment supercapacitors include the low potential of the operating voltage (U _slave ≤1V). This is due to the fact that organic polymer membranes impregnated with acid solutions that have a low electrochemical decomposition potential (U _decomp. ≤1 V) are used as electrolytes.

The results of our studies have shown [2. ASUlihin, NFUvarov, Yu.G. Mateyshina, LIBrezhneva, AAMatvienko "Composite solid electrolytes LiC1O ₄ -Al ₂ O ₃ " Solid State Ionics 177 (2006) 2787-2790], that composite solid electrolytes can be used as lithium-conducting materials Based on lithium perchlorate LiClO ₄ . This electrolyte is lithium perchlorate doped with γ-alumina with a specific surface area of ~ 200 m / g. These electrolytes have high ionic conductivity (not less than 10 ^-3 S / cm at T = 200 ° C) and a high value of the electrochemical decomposition potential (the decomposition potential of lithium perchlorate in a composite solid electrolyte in vacuum is 3.5-4V).

The closest technical solution to the claimed is a supercapacitor with a highly conductive solid electrolyte CsAg ₄ Br _3-x I _2-x , where 0≅X≅0.8 (3. Pat. RU No. 2012105, Application No. 4942624/21, publ. 30.04. 1994). However, the manufacture of this supercapacitor requires the use of precious metals, which significantly increases their cost. Its manufacture is carried out by the method of pulsed thermal evaporation at evaporator temperatures in the range of 850-1050K, which leads to an increase in energy consumption.

The problem solved by the claimed technical solutions is to develop a supercapacitor with a composite inorganic solid electrolyte having thermal stability in a wide temperature range, high operating voltage potential, high value of the accumulated charge, as well as low energy consumption for its manufacture.

The problem is solved due to the fact that in the inventive supercapacitor with an inorganic composite solid electrolyte, including electrodes separated by a highly conductive solid electrolyte, the positive and negative electrodes are made of a composite containing nanoscale oxide LiMn _{2 x} Me _x O ₄ , where Me = Ni ²⁺ , Mn ^3+, composite solid electrolyte and conductive carbon black, the solid electrolyte is made of a composite solid electrolyte lithium perchlorate 0.4LiClO ₄ - 0.6Al ₂ O ₃ and current feeder is composed of two pla tin nickel metal attached to the outer sides of the electrodes.

This supercapacitor is symmetrical, since the negative and positive electrodes are made of the same material.

Salient features of this technical solution in relation to the prototype are:

- the positive and negative electrodes are made of a composite containing nanosized oxide LiMn _{2 x} Me _x O ₄ , where Me = Ni ²⁺ , Mn ³⁺ , solid electrolyte and electrically conductive soot;

- solid electrolyte is made of a composite solid electrolyte based on lithium perchlorate 0.4LiClO ₄ - 0.6Al ₂ O ₃ ;

- the current supply consists of two plates of metallic nickel mounted on the outer sides of the electrodes.

The problem is solved due to the fact that in the inventive supercapacitor with an inorganic composite solid electrolyte, including electrodes separated by a highly conductive solid electrolyte, the positive electrode is made of a composite containing nanoscale oxide LiMn _{2 x} Me _x O ₄ , where Me = Ni ²⁺ , Mn ^3+, LiMn _2-x Me _x O _4, where Me = Ni ^2+, Mn ^3+, composite solid electrolyte and conductive carbon black, and the negative electrode is made of a composite comprising nanoscale manganese oxide is MnO _2, the composite solid electrolyte, and e ktroprovodyaschuyu carbon black, the solid electrolyte is made of a composite based solid electrolyte lithium perchlorate 0.4LiSlO ₄ - 0.6Al ₂ O ₃ and current feeder is composed of two nickel metal plates attached to the outer sides of the electrodes.

This supercapacitor is asymmetric, since the negative and positive electrodes are made of different materials.

Salient features of the second claimed technical solution in relation to the prototype are:

- the positive electrode is made of a composite containing nanoscale oxide LiMn _{2 x} Me _x O ₄ , where Me = Ni ²⁺ , Mn ³⁺ , solid electrolyte and electrically conductive soot;

- the negative electrode is made of a composite containing nanoscale manganese oxide MnO ₂ , a solid electrolyte and electrically conductive soot;

- solid electrolyte is made of a composite solid electrolyte based on lithium perchlorate 0.4LiClO ₄ - 0.6Al ₂ O ₃ ;

- the current supply consists of two plates of metallic nickel mounted on the outer sides of the electrodes.

The analysis of the prior art, including a search by patent and scientific and technical sources of information, made it possible to establish that the totality of the distinguishing features of the claimed technical solutions were not found in the prior art, which allows us to conclude about the novelty and inventive step of the claimed supercapacitors.

Figure 1 schematically shows a supercapacitor with an inorganic composite solid electrolyte, made in the form of an electrochemical cell, consisting of five layers with a thickness of each layer of not more than 100 μm, including positive and negative electrodes 1 made of a composite containing nanoscale LiMn oxide ₂ Me _x O ₄ , where Me = Ni ²⁺ , Mn ³⁺ , composite solid electrolyte and electrically conductive soot in the case of a symmetric supercapacitor. In asymmetric execution of the supercapacitor, the negative electrode is made of a composite comprising nanosized manganese oxide MnO ₂ , a composite solid electrolyte, and electrically conductive soot. Solid electrolyte 2 is made of a composite solid electrolyte based on lithium perchlorate 0.4LiClO ₄ - 0.6Al ₂ O ₃ and placed between the electrodes 1 of the inventive supercapacitor. The current lead 3 consists of two plates of metallic nickel, mounted on the outer sides of the electrodes. The supercapacitor is made by hot pressing.

The properties of the claimed inventions are demonstrated in the examples below.

Example 1

LiMn oxide _1.5 Ni _0.05 O ₄ , composite solid electrolyte 0.4LiСlО ₄ - 0.6Al ₂ O ₃ and electrically conductive carbon black, taken in a weight ratio of 3: 6: 1, are thoroughly mixed and heated at a temperature of 150 ° С for 30 min. A composite solid electrolyte 0.4LiСlО ₄ - 0.6Al ₂ O _{3 was} taken as an ion-conducting membrane. Nickel metal was used as a current lead. Using the obtained electrode composite, composite solid electrolyte and metallic nickel form a symmetric electrochemical cell consisting of five layers of Ni / LiMn _1.5 Ni _0.05 04 / 0.4LiC1O ₄ -0.6Al ₂ O ₃ / LiMn _1.5 Ni _0.05 O ₄ / Ni with the thickness of each layer no more than 100 microns. A schematic representation of a supercapacitor is shown in FIG. Measurement of electrochemical properties is carried out in vacuum. The specific capacitance value was calculated using the method of galvanostatic charge-discharge cycling at a current density of 0.05 A / g per gram of oxide used, which is 6.8 F / g at a temperature of 95 ° C and 24.1 F / g at a temperature of 150 ° C.

Example 2

Cathode and anode materials are being prepared. The cathode material is a composite consisting of LiMn _i.5 Ni _0.45 Mg _0.05 O ₄ oxide, 0.4LiClO ₄ - O.6Al ₂ O ₃ composite solid electrolyte and electrically conductive soot, taken in a weight ratio of 3: 6: 1, carefully mixed and warmed up at a temperature of 150 ° C. The cathode material is a composite containing manganese oxide MnO ₂ , a composite solid electrolyte 0.4LiClO ₄ - O.6Al ₂ O ₃ and electrically conductive soot, taken in a weight ratio of 3: 6: 1, thoroughly mixed and heated at a temperature of 150 ° C . Using the obtained cathode and anode materials Ni / LiMn _1.5 Ni _0.45 Mg _0.05 O ₄ /0.4LiСlО ₄ - 0.6Al ₂ O _3, an electrochemical cell is formed consisting of five layers with a thickness of each layer of not more than 100 μm. A schematic representation of a supercapacitor is shown in FIG. Measurement of electrochemical properties is carried out in vacuum. The specific capacitance value is calculated using the method of galvanostatic charge-discharge cycling at a current density of 0.05 A / g per gram of oxide used, is 3.5 F / g at a temperature of 25 ° C and 25.5 F / g at a temperature of 150 ° C.

The inventive supercapacitors differ from other known ones in that they use a composite solid inorganic electrolyte based on lithium perchlorate 0.4LiClO ₄ - 0.6Al ₂ O ₃ with a high electrochemical decomposition potential (U _decomp. > 3V) as an electrolyte. They do not contain organic compounds, due to which they are resistant to thermal effects (operating temperature range T _work = 25-250 ° C).

The technical result of the claimed technical solution is the development of symmetric and asymmetric supercapacitor with solid inorganic composite lithium conducting electrolyte which provides high performance, namely thermal stability in the temperature range 25-250 ° C, high potential _slave operating voltage U> 1B and high capacity .

Claims (2)

1. A supercapacitor with an inorganic composite solid electrolyte, comprising electrodes separated by a highly conductive solid electrolyte, characterized in that the positive and negative electrodes are made of a composite containing nanoscale oxide LiMn _{2 x} Me _x O ₄ , where Me = Ni ²⁺ , Mn ^{3 +,} composite solid electrolyte and conductive carbon black, separated by highly conductive solid electrolyte made of a solid electrolyte composite based on lithium perchlorate 0.4LiClO ₄ -0.6Al ₂ O ₃ and current feeder is composed of two layers nickel metal attached to the outer sides of the electrodes. 2. A supercapacitor with an inorganic composite solid electrolyte, comprising electrodes separated by a highly conductive solid electrolyte, characterized in that the positive electrode is made of a composite containing nanoscale oxide LiMn _{2 x} Me _x O ₄ , where Me = Ni ²⁺ , Mn ³⁺ , composite solid electrolyte and conductive carbon black, and the negative electrode is made of a composite comprising nanoscale manganese oxide is MnO _2, the composite solid electrolyte and conductive carbon black, the solid electrolyte is made of a composite th based solid electrolyte lithium perchlorate 0.4LiClO ₄ -0.6Al ₂ O ₃ and current feeder is composed of two nickel metal plates attached to the outer sides of the electrodes.