CN101483254A - Water system lithium cell electrolyte solution capable of film forming on lithium surface - Google Patents
Water system lithium cell electrolyte solution capable of film forming on lithium surface Download PDFInfo
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- CN101483254A CN101483254A CNA2008100520119A CN200810052011A CN101483254A CN 101483254 A CN101483254 A CN 101483254A CN A2008100520119 A CNA2008100520119 A CN A2008100520119A CN 200810052011 A CN200810052011 A CN 200810052011A CN 101483254 A CN101483254 A CN 101483254A
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- lithium
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- water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a water system lithium battery electrolyte capable of forming a film on a lithium surface comprising an alkalis, water and an additive agent characterized in that: the additive agent is an organic matter containing a (-CH2-O-CH2-) group and an derived organic salt; the additive agent has a basic formula of R1(-CH2-O-CH2-)R2, wherein R1 and R2 are organic groups, the carbon numbers in the R1 and R2 are all within 1-20, and the R1 and R2 can also contain O, P, N, S and F elements. Because the additive agent added to the water system lithium battery electrolyte and the metal lithium can occur an interfacial reaction, and form quickly the film on the metal lithium at the surface film broken part, substantially suppress the reaction of the metal lithium and water, reduce the lithium and water side reaction speed, reduce the hydrogen and the reaction heat release caused by the corrosion due to the broke of the surface film of the metal lithium and improve the use efficiency of the lithium electrode and the battery safety.
Description
Technical field
The invention belongs to the water system lithium cell technical field, particularly relate to a kind of can be at the water system lithium cell electrolyte solution of lithium surface filming.
Background technology
Lithium metal battery has high specific energy and specific capacity, is the emphasis of new forms of energy research for a long time always.The electrolyte system that lithium battery adopted mainly is the non-aqueous solution electrolysis liquid system, soon the organic or inorganic lithium salts is dissolved in some organic solvents and forms electrolyte, adopt the lithium battery of non-aqueous solution electrolysis liquid system that multiple commercial prod has been arranged, be used widely in a lot of fields.But often there are following problems in non-aqueous system: cause the high power performance of battery relatively poor owing to the ionic conductivity of organic system electrolyte is bad; The organic system temperature influence obviously causes the high temperature performance of battery bad; The preparation of organic system electrolyte is strict, and cost is higher; Organic system electrolyte environment friendly is undesirable, often contains toxic component etc.
And the electrolyte of the lithium battery of water-based system has adopted water solution system, and the electrolyte of water solution system has higher conductivity and is fit to high power discharge; High and low temperature resistance is good; With low cost, advantages of environment protection.Simultaneously, adopt water solution system can also make to be with water reactant lithium addition, the weight of water can be disregarded in fields such as navigation, so such battery has high specific energy and specific capacity, in marine use, have very large attraction and bright prospects, but because of violent corrosion reaction takes place between lithium metal meeting and the water, generation is burnt or is exploded and causes danger easily.
At present; the corrosion reaction of disclosed inhibition lithium metal in the aqueous solution is the diaphragm that forms the well behaved lithium ion conducting of one deck on the lithium metal surface in advance; there has been this layer diaphragm lithium metal both can discharge work in water solution system; can avoid again and water between electron transport, prevented the generation of corrosion reaction.But along with the carrying out of lithium metal discharge process, above-mentioned this tunic can inevitably break, and the effect of diaphragm was lost efficacy, and violent corrosion reaction takes place for the lithium metal and the aqueous solution that expose below the rete, same the danger of burning or exploding takes place easily.
Summary of the invention
The present invention provides a kind of and has prevented that lithium battery burning and a kind of of blast can be at the water system lithium cell electrolyte solutions of lithium surface filming for solving problems of the prior art.
The present invention for solving the technical scheme that technical problem adopted that exists in the known technology is:
Can comprise alkali, water and additive at the water system lithium cell electrolyte solution of lithium surface filming, be characterized in: described additive is for containing (CH
2-O-CH
2-) organic substance of group and the organic salt of deriving thereof.
The present invention can also adopt following technical measures to realize:
Can be characterized at the water system lithium cell electrolyte solution of lithium surface filming: described additive basic structure formula is R
1(CH
2-O-CH
2-) R
2, R wherein
1And R
2Be organic group, R
1And R
2In a carbon atom number average in 1-20, R
1And R
2In also can comprise O, P, N, S, F element.
Can be characterized at the water system lithium cell electrolyte solution of lithium surface filming: described R
1And R
2Can comprise one or more (CH
2-O-CH
2-) group, R
1And R
2In also can comprise K, Na, Li element.
Can be at the water system lithium cell electrolyte solution of lithium surface filming, be characterized in: the concentration of described alkali is every liter of 1.5M～15M mole, described content of additive is 0.1～100 grams per liter, can suitably heat to accelerate the dissolving of muddiness or precipitation in the electrolyte quota process.
Can be characterized at the water system lithium cell electrolyte solution of lithium surface filming: the concentration of described alkali is 7～12 moles every liter, and described content of additive is 0.5～10 grams per liter.
Can be characterized at the water system lithium cell electrolyte solution of lithium surface filming: described alkali is one or more mixtures in potassium hydroxide, NaOH, the lithium hydroxide.
Can be characterized at the water system lithium cell electrolyte solution of lithium surface filming: described additive is diethylene glycol or triethanolamine.
Advantage and good effect that the present invention has are: owing to added a kind of additive in water system lithium cell electrolyte solution, this additive can with lithium metal generation interfacial reaction, rapid film forming on the lithium metal of skin covering of the surface rent, the reaction, the reduction lithium water side reaction speed that significantly suppress lithium metal and water, reduce the corrosion releasing hydrogen gas and the reaction heat that break and cause owing to the lithium metal skin covering of the surface, improve the service efficiency and the battery security of lithium electrode.
Description of drawings
Fig. 1 exposes the lithium metal schematic diagram for water system lithium cell lithium surface protection film rupture;
Fig. 2 the present invention can suppress lithium corrosion schematic diagram at the water system lithium cell electrolyte solution of lithium surface filming;
Fig. 3 is that do not have can be at the water system lithium cell electrolyte solution of lithium surface filming, and lithium metal and water vigorous reaction are emitted a large amount of hydrogen and heat schematic diagram;
Fig. 4 is lithium electrode cyclic voltammetric test maximum discharge current figure among the embodiment 1;
Fig. 5 is lithium electrode cyclic voltammetric test maximum discharge current figure among the embodiment 2.
Label among the figure is respectively: 1. diaphragm; 2. lithium metal; 3. additive forms film on the lithium surface in the electrolyte; 4. lithium metal and the water vigorous reaction a large amount of hydrogen and the heat of emitting.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, enumerate following examples now, and conjunction with figs. is described in detail as follows:
Please refer to Fig. 1-Fig. 5: Fig. 1 is the lithium metal 2 of lithium ion diaphragm 1 protection, the process of discharging in the aqueous solution; Fig. 2 has taken place to break for working as diaphragm 1 among Fig. 1, contains (CH owing to exist
2-O-CH
2-) organic substance of group and the organic salt of deriving thereof is as the electrolyte of additive, can make in the electrolyte additive form film 3 rapidly on the lithium surface, because lithium metal 2 surface filmings and significantly stoping corrode between lithium metal 2 and the water, obviously suppress the corrosion reaction between the water in lithium metal 2 and the electrolyte, reduce the hydrogen that this reaction is emitted, not only improve the useful life of electrode utilance and electrolyte, the more important thing is the release that has also reduced this reaction heat when suppressing the lithium metal corrosion reaction, and improve the security performance of battery.Make surface protection film can continue to play a role; Fig. 3 has taken place to break for working as diaphragm 1 among Fig. 1, does not add in the electrolyte and contains (CH
2-O-CH
2-) organic substance of group and the organic salt additive of deriving thereof, diaphragm 1 a large amount of hydrogen and the heat 4 that the lithium metal that to expose and water vigorous reaction are emitted that break.
Embodiment 1: with KOH as the used highly basic of aqueous electrolyte, make 8 moles every liter aqueous slkali, add the diethylene glycol of 10 grams per liters then in this aqueous slkali, it is fully dissolved, preparing the present invention can be at the water system lithium cell electrolyte solution of lithium surface filming.
Embodiment 2: as the used highly basic of aqueous electrolyte, make 8 moles every liter aqueous slkali with KOH, add the triethanolamine of 5 grams per liters then in this aqueous slkali, it is fully dissolved, preparing the present invention can be at the water system lithium cell electrolyte solution of lithium surface filming.
Fig. 4 is that present embodiment 1 makes the experimental result that electrolyte carries out cyclic voltammetry experiment test metal lithium electrode maximum discharge current therein; Fig. 5 is that present embodiment 2 makes the experimental result that electrolyte carries out cyclic voltammetry experiment test metal lithium electrode maximum discharge current therein.As seen from the figure, the maximum current of lithium electrode has reflected the kinetics ability of lithium metal in this solution in the different electrolytes, and it is active more in this solution to obtain big more maximum discharge current explanation lithium electrode, easy more and electrolyte generation corrosion reaction.On the contrary, can stop the reaction between lithium metal and the water if lithium metal surface forms certain stable skin covering of the surface, the maximum operating currenbt of lithium electrode under this situation is significantly descended.That is to say, if can reflect the effect of additive with maximum discharge current density in the lithium electrode surface film forming---the additive component in the electrolyte can be at the lithium metal surface filming, and the maximum discharge current density of lithium electrode also can obviously reduce.Obviously, at the 0-1V of metal lithium electrode vs.Li
+In/Li the operating voltage range, the GOLD FROM PLATING SOLUTION that adds additive belongs to the maximum discharge current density of lithium electrode will be significantly less than non-additive situation.The adding of additive makes the maximum discharge current of lithium electrode almost have only 40% when additive-free, and the existence of additive makes the obvious inhibition of having arrived of speed lithium metal corrosion reaction faster originally.Illustrate this additive can be on metal lithium electrode film forming rapidly, effectively suppress the corrosion reaction of lithium metal in aqueous electrolyte and between the water.And lithium electrode just is applied in certain current density in a short period of time when actual battery discharges, be different from that electric current rises gradually in the cyclic voltammetry experiment, the effect meeting of additive is more obvious in the actual discharge process generally speaking, can make maximum discharge current drop to about 30% of additive-free condition.
In the above preparation process, can make the electrolyte that the aqueous lithium battery is used with additive and alkali are soluble in water, also can will add additive again after the alkali dissolving earlier, also can earlier additive be dissolved in a certain amount of water in being added to alkali lye; Can suitably heat to accelerate the dissolving of muddiness or precipitation in the electrolyte quota process.
Claims (7)
1. one kind can comprise alkali, water and additive at the water system lithium cell electrolyte solution of lithium surface filming, and it is characterized in that: described additive is for containing (CH
2-O-CH
2-) organic substance of group and the organic salt of deriving thereof.
2. according to claim 1 can it is characterized in that at the water system lithium cell electrolyte solution of lithium surface filming: described additive basic structure formula is R
1(CH
2-O-CH
2-) R
2, R wherein
1And R
2Be organic group, R
1And R
2In a carbon atom number average in 1-20, R
1And R
2In also can comprise O, P, N, S, F element.
3. according to claim 2 can it is characterized in that: described R at the water system lithium cell electrolyte solution of lithium surface filming
1And R
2Can comprise one or more (CH
2-O-CH
2-) group, R
1And R
2In also can comprise K, Na, Li element.
4. according to claim 1 can be at the water system lithium cell electrolyte solution of lithium surface filming, it is characterized in that: the concentration of described alkali is every liter of 1.5M～15M mole, described content of additive is 0.1～100 grams per liter, can suitably heat to accelerate the dissolving of muddiness or precipitation in the electrolyte quota process.
5. according to claim 1 can it is characterized in that at the water system lithium cell electrolyte solution of lithium surface filming: the concentration of described alkali is 7～12 moles every liter, and described content of additive is 0.5～10 grams per liter.
6. according to claim 1 can it is characterized in that at the water system lithium cell electrolyte solution of lithium surface filming: described alkali is one or more mixtures in potassium hydroxide, NaOH, the lithium hydroxide.
7. according to claim 1 can it is characterized in that at the water system lithium cell electrolyte solution of lithium surface filming: described additive is diethylene glycol or triethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100520119A CN101483254A (en) | 2008-01-07 | 2008-01-07 | Water system lithium cell electrolyte solution capable of film forming on lithium surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100520119A CN101483254A (en) | 2008-01-07 | 2008-01-07 | Water system lithium cell electrolyte solution capable of film forming on lithium surface |
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| Publication Number | Publication Date |
|---|---|
| CN101483254A true CN101483254A (en) | 2009-07-15 |
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ID=40880257
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|---|---|---|---|
| CNA2008100520119A Pending CN101483254A (en) | 2008-01-07 | 2008-01-07 | Water system lithium cell electrolyte solution capable of film forming on lithium surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105990606B (en) * | 2015-02-13 | 2019-03-12 | 北京大学深圳研究生院 | A kind of lithium ion battery |
-
2008
- 2008-01-07 CN CNA2008100520119A patent/CN101483254A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105990606B (en) * | 2015-02-13 | 2019-03-12 | 北京大学深圳研究生院 | A kind of lithium ion battery |
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| PB01 | Publication | ||
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Open date: 20090715 |