CN1512518A - A kind of composite electrolyte and its application - Google Patents

Abstract

This invention relates to a complex electrolyte and its usage which is an alcohol addition compound electrolyte generated by alcohol and polybase metallic salt halide or added by at least one of elementary iodine, control agent for rate of crystallization or monad nantokite compound having high conductivity, non-volatility and suitable fusion point used in solar energy battery, Li ion battery and fuel battery.

Description

A kind of composite electrolyte and its application

technical field

The invention relates to an electrolyte material that can be used in solar cells, lithium ion batteries, fuel cells, etc. and its application, especially a composite electrolyte and its application.

Background technique

Electrolyte materials with high conductivity and stable performance can be used as electrolytes for various batteries and have broad application prospects. Common inorganic polycrystalline solid-state electrolytes or glass materials have low conductivity, while liquid electrolytes have electrolyte leakage and packaging technical problems. These factors limit the efficiency improvement of the battery. The search for high-conductivity solid-state electrolytes and non-volatile highly-conductive molten-salt electrolytes has aroused widespread interest. Fast ionic conductors and polymer ionic conductors have attracted great attention. In 1986, B.Schoch, E.Hartmann, and W.Weppner wrote in the Journal of Solid State Ionics (Solid State Ionics, 18 & 19(1986), 529); W.Weppner, W.Wlzel R.Kniep and A.Rabenau, "German Applied Chemistry" (Angew, Chem.Int.Ed.Engl.25(12, 1087(1986)); Ran Yujun, Chen Guanxiong, Chen Liquan, Sichuan University Journal (Natural Science Edition) Volume 25, Issue 4, 450 (1988) and other research groups successively studied the alcohol addition compounds generated by alcohols and lithium halide salts (LiX, X=Cl, Br, I), and measured them electrical properties and crystal structure. The conductivity of this simple alcohol addition compound is only 10 ^-4 Scm ^-1 , which cannot meet the requirements of practical applications. Another disadvantage of this type of alcohol addition compound is that the crystallization rate is too fast , the crystal grains formed during practical application reach the order of hundreds of microns to millimeters, and the contact between such large grains and the contact between the electrolyte and the electrode are very poor, which is an important factor affecting the efficiency of the dielectric and the efficiency of the battery. Therefore, it has Electrolytes with high conductivity, non-volatility and suitable melting point will be widely and practically used in the field of batteries.

Contents of the invention

The object of the present invention is to provide a composite electrolyte with high electrical conductivity and suitable melting point in order to overcome the problems existing in the prior art.

Another object of the present invention is to provide a composite electrolyte that can be applied to solar cells, lithium ion batteries, and fuel cells.

The purpose of the present invention can be achieved through the following measures:

A composite electrolyte, the formula of the composite electrolyte is:

M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w +aI ₂ +bB+cC

In the formula, M ¹ , M ² , M ³ , and M ⁴ are selected from one of the alkali metal elements Li, Na, K, Ru, and Cs respectively, wherein x, y, z, and v are atomic parts, and 0≤( x, y, z, v)≤1 and x+y+z+v=1; N is selected from one of the halogen elements F, Cl, Br, I; A is alcohol or its derivatives, wherein w= 1～4; B is selected from at least one of the substances that can inhibit the crystallization rate of M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w ; C is a monovalent copper salt compound CuX, wherein X is selected from One of F, Cl, Br, I, SCN, CN; a=0~0.2mol; b=0~0.2mol; c=0~0.2mol.

When A is a monohydric alcohol, w=4; when A is a dihydric alcohol, w=2; when A is a tetrahydric alcohol, w=1.

The B is selected from at least one of ceramic powder TiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , γ-LiAlO ₂ , MgO, SiO ₂ , and SnO ₂ .

The composite electrolyte is preferably Li _β M _1-β I·(A) _w +aI ₂ +bB+cC; wherein M is selected from one of the alkali metal elements Li, Na, K, Ru, and Cs, and β is an atomic part Number, 0≤β≤1; A is alcohol or its derivatives, w=1～4; B is selected from at least one of the substances that can inhibit the crystallization rate of _{LiβM1 -βI} ·(A) _w ; C is a monovalent copper salt compound CuX, wherein X is selected from one of F, Cl, Br, I, SCN and CN; a=0-0.2mol; b=0-0.2mol; c=0-0.2mol.

An application of a composite electrolyte, which can be applied to solar cells, lithium ion batteries, and fuel cells.

Compared with the prior art, the present invention has the following advantages: the performance of the composite electrolyte is stable, the conductivity is high, and the melting point is suitable; by adjusting the ratio of different components, the physical properties of this type of composite electrolyte, such as melting point and conductivity, can be effectively adjusted. Therefore, the composite electrolyte has a wider application field.

Detailed ways

The general formula of the alcohol addition compound produced by the alcohols and the halogenated polyalkali metal salts of the present invention is M ¹ _x M ² _y M ³ _n M ⁴ _v N (A) _w , where M ¹ , M ² , M ^{3. M4} is selected from one of the alkali metal elements Li, Na, K, Ru, and Cs, wherein x, y, z, and v are atomic parts, and 0≤(x, y, z, v)≤ 1 and x+y+z+v=1; N is selected from one of the halogen elements F, Cl, Br and I; A is alcohol or its derivatives, wherein w=1-4. Its embodiment sees embodiment 1 and 2 in table 1.

In order to improve the conductivity of the electrolyte, we have invented a composite electrolyte in which an alcohol addition compound formed from alcohols and polyalkali metal halides is doped with iodine. Its general formula is:

M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w + aI ₂

In the formula, M ¹ , M ² , M ³ , and M ⁴ are selected from one of the alkali metal elements Li, Na, K, Ru, and Cs, wherein x, y, z, and v are atomic parts, and 0≤( x, y, z, v)≤1 and x+y+z+v=1; N is selected from one of the halogen elements F, Cl, Br, I; A is alcohol or its derivatives, wherein w= 1～4; a=0～0.2mol. By introducing iodine to increase the defects of the electrolyte crystal, the ionic conductivity of the electrolyte is increased. Examples are shown in Examples 3, 4 and 5 in Table 1, and their electrical conductivities are respectively 2.1×10 ^-3 S/cm, 1.8×10 ^-3 S/cm and 1.5×10 ^-3 S/cm, obviously superior to Conductivity of Alcohol Addition Compound Electrolytes in the Prior Art. See Table 2-10 for other embodiments.

The present invention controls the crystallization rate of the electrolyte by adding the control agent B to the alcohol addition compound or the alcohol addition compound mixed with iodine simple substance, so that the crystallization rate of the solid composite electrolyte is greatly reduced, and nano crystallization is realized. , to further improve the sufficient contact between the solid composite electrolyte and the porous electrode interface. The general formula of the composite electrolyte added with control agent B is:

M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w +bB; and

M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w +aI ₂ +bB

In the formula, M ¹ , M ² , M ³ , and M ⁴ are selected from one of the alkali metal elements Li, Na, K, Ru, and Cs, wherein x, y, z, and v are atomic parts, and 0≤( x, y, z, v)≤1 and x+y+z+v=1; N is selected from one of the halogen elements F, Cl, Br, I; A is alcohol or its derivatives, wherein w= 1~4; B is at least one selected from the substances that can inhibit the crystallization rate of M ¹ XM ² _y M ³ _z M ⁴ _v N·(A) _w a=0~0.2mol; b=0~0.2mol. Examples of M ¹ _x M ² _y M ³ _z M ⁴ _v N·(A) _w +bB electrolytes are shown in 6, 7 and 8 in Table 1. Examples of M ¹ _x M ² _y M ³ _z M ⁴ _v N·(A) _w +aI ₂ +bB electrolytes are shown in 12, 13 and 14 in Table 1, and their electrical conductivities are 1.3×10 ^-3 S/ cm, 2.1×10 ^-3 S/cm, 3.2×10 ^-3 S/cm. See Table 2-10 for other embodiments.

In order to achieve a composite electrolyte with higher conductivity and stable performance, the present invention is based on alcohol addition compounds, alcohol addition compounds doped with iodine simple substance, alcohol addition compounds adding control agent B and adding control agent B and Monovalent copper salt compounds are added to the alcohol addition compounds doped with iodine element, in order to further improve the conductivity of the electrolyte through the synergistic effect of different cations. Its general formula is respectively:

M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w +cC;

M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w +aI ₂ +cC;

M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w +bB+cC; and

M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w +aI ₂ +bB+cC

In the formula, M ¹ , M ² , M ³ , and M ⁴ are selected from one of the alkali metal elements Li, Na, K, Ru, and Cs, wherein x, y, z, and v are atomic parts, and 0≤( x, y, z, v)≤1 and x+y+z+v=1; N is selected from one of the halogen elements F, Cl, Br, I; A is alcohol or its derivatives, wherein w= 1～4; B is selected from at least one of the substances that can inhibit the crystallization rate of M ¹ _x M ² _y M ³ _z M ⁴ _v N (A) _w ; C is a monovalent copper salt compound CuX, wherein X is selected from One of F, Cl, Br, I, SCN, CN; a=0~0.2mol; b=0~0.2mol; c=0~0.2mol.

Examples of M ¹ _x M ² _y M ³ _z M ⁴ _v N·(A) _w +cC composite electrolytes are shown in Examples 9, 10 and 11 in Table 1; their electrical conductivity is 9.1×10 ^-3 S/cm , 11.5×10 ^-3 S/cm and 16.8×10 ^-3 S/cm. See Table 2-10 for other embodiments.

Examples of M ¹ _x M ² _y M ³ _z M ⁴ _v N·(A) _w +aI ₂ +cC composite electrolytes are shown in Examples 15, 16 and 17 in Table 1; their electrical conductivity is 6.3×10 ^-3 S/cm, 7.5×10 ^-3 S/cm, and 8.2×10 ^-3 S/cm. See Table 2-10 for other embodiments.

Examples of M ¹ _x M ² _y M ³ _z M ⁴ _v N·(A) _w +bB+cC composite electrolytes are shown in Examples 18, 19 and 20 in Table 1; their electrical conductivity is 4.3×10 ^-3 S /cm, 3.7× ^{10 -3} S/cm and 3.2×10 ^-3 S/cm. See Table 2-10 for other embodiments.

The examples of M ¹ _x M ² _y M ³ _z M ⁴ _v N·(A) _w +aI ₂ +bB+cC composite electrolytes are shown in Examples 21-26 in Table 1; the conductivity of Examples 21-23 is as follows: 6.3, 7.5 and 8.2; the conductivity of Examples 25 and 26 are 3.7×10 ^-3 S/cm and 3.2×10 ^-3 S/cm respectively. See Table 2-10 for other embodiments.

Therefore, the addition of monovalent copper salt compound CuX can significantly improve the conductivity of the composite electrolyte.

In each embodiment in the following table 1, M ¹ is Li, M ² is K or Na, z and v in M ³ _z and M ⁴ _v are 0, N is iodine I, A _y is methanol, y=4, B is TiO ₂ , C is CuI; "-" in the table indicates the data to be tested.

Table 1:

M ¹ _x of each embodiment in the following table 2 is Li, y, z and v in M ² _y , M ³ _z , M ⁴ _v are 0, N is iodine I, A _y is methanol, y=4, B is ZnO, C is CuBr; "-" in the table indicates the data to be tested.

Table 2

In each embodiment in the following table 3, M ¹ _x is Li, y, z and v in M ² _y , M ³ _z , M ⁴ _v are 0, N is iodine I, A _y is methanol, y=4, B is Al ₂ O ₃ , C is CuSCN; "-" in the table indicates the data to be tested.

table 3

M ¹ _x of each embodiment in the following table 4 is Li, y, z and v in M ² _y , M ³ _z , M ⁴ _v are 0, N is iodine I, A _y is ethanol, y=4, B is TiO ₂ , C is CuI; "-" in the table indicates the data to be tested.

Table 4:

In each embodiment in the following table 5, M ¹ _x is Li, M ² _y is Na, z and v in M ³ _z and M ⁴ _v are 0, N is iodine I, A _y is ethanol, y=4, B is TiO ₂ , C is CuI; "-" in the table indicates the data to be tested.

table 5:

M ¹ _x of each embodiment in the following table 6 is Li, y, z and v in M ² _y , M ³ _z , M ⁴ _v are 0, N is bromine Br, A _y is methanol, y=4, B is TiO ₂ , C is CuI; "-" in the table indicates the data to be tested.

Table 6:

In each embodiment in the following table 7, M ¹ _x is Li, y, z and v in M ² _y , M ³ _z , M ⁴ _v are 0, N is bromine Br, A _y is methanol, y=4, B is Al ₂ O ₃ , C is CuBr; "-" in the table indicates the data to be tested.

Table 7

In each example in Table 8 below, M ¹ _x is Li, y, z and v in M ² _y , M ³ _z , and M ⁴ _v are 0, N is bromine Br, A _y is methanol, y=4, B is SiO ₂ , C is CuSCN; "-" in the table indicates the data to be tested.

Table 8

M ¹ _x of each embodiment in the following table 9 is Li, y, z and v in M ² _y , M ³ _z , M ⁴ _v are 0, N is bromine Br, A _y is ethanol, y=4, B is TiO ₂ , C is CuI; "-" in the table indicates the data to be tested.

Table 9:

In each embodiment in the following table 10, M ¹ _x is Li, M ² _y is Na, z and v in M ³ _z and M ⁴ _v are 0, N is bromine Br, A _y is ethanol, y=4, B is TiO ₂ , C is CuI; "-" in the table indicates the data to be tested.

table 5:

The conductivity σ measured in the above examples is mostly on the order of 10 ^-3 S/cm, and the conductivity of Examples 10 and 11 reaches the order of 10 ^-2 S/cm, which are better than the existing alcohols and alcohols of alkali metal halides Conductivity of addition-like compounds.

Taking Example 12 as an example, the preparation process of the composite electrolyte of the present invention is briefly described: respectively weigh iodine and titanium dioxide in a molar ratio of 0.0005:0.0025, add them to anhydrous methanol solution, and stir to make them fully dissolved and dispersed; Measure a certain amount of anhydrous lithium iodide; by the amount of said anhydrous lithium iodide, measure the required methanol mixed solution containing iodine and titanium dioxide; slowly add the above mixed solution in the anhydrous lithium iodide, Lithium iodide was gradually dissolved in the above mixed solution, a chemical reaction occurred and heat was released, and the composite electrolyte of Example 12 was generated. The composite electrolytes of other examples all adopt the preparation method of Example 12, and only need to adjust each required substance and its content.

Claims (5)

1. composite electrolyte, the formula of this composite electrolyte is:

M ¹ _xM ² _yM ³ _zM ⁴ _vN·(A) _w+aI ₂+bB+cC

M in the formula ¹, M ², M ³, M ⁴Be selected from alkali metal Li respectively, Na, K, Ru, a kind of among the Cs, x wherein, y, z, v is the atom umber, 0≤(x, y, z, v)≤1 and x+y+z+v=1; N is selected from a kind of among halogen F, Cl, Br, the I; A is pure or derivatives thereof, wherein w=1～4; B is selected from and can suppresses M ¹ _xM ² _yM ³ _zM ⁴ _vN (A) _wThe material of crystalline rate at least a; C is cuprous salt Compound C uX, and wherein X is selected from a kind of among F, Cl, Br, I, SCN, the CN; A=0～0.2mol; B=0～0.2mol; C=0～0.2mol.

2. composite electrolyte as claimed in claim 1 is characterized in that, w=4 when described A is monohydric alcohol; W=2 when A is dihydroxylic alcohols; W=1 when A is tetrahydroxy alcohol.

3. composite electrolyte as claimed in claim 1 is characterized in that described B is selected from ceramic powders TiO ₂, ZnO, ZrO ₂, Al ₂O ₃, γ-LiAlO ₂, MgO, SiO ₂, SnO ₂In at least a.

4. composite electrolyte as claimed in claim 1 is characterized in that, this composite electrolyte is Li _βM _1-βI (A) _w+ aI ₂+ bB+cC; Wherein M is selected from alkali metal Li, Na, and K, Ru, a kind of among the Cs, β is the atom umber, 0≤β≤1; A is pure or derivatives thereof, w=1～4; B is selected from and can suppresses Li _βM _1-βI (A) _wThe material of crystalline rate at least a; C is cuprous salt Compound C uX, and wherein X is selected from a kind of among F, Cl, Br, I, SCN, the CN; A=0～0.2mol; B=0～0.2mol; C=0～0.2mol.

5, the application of the described composite electrolyte of a kind of claim 1 is characterized in that, this composite electrolyte can be applicable to solar cell, lithium ion battery, fuel cell.