CN105789699A - Lithium secondary battery and preparation method thereof as well as lithium secondary battery electrolyte - Google Patents
Lithium secondary battery and preparation method thereof as well as lithium secondary battery electrolyte Download PDFInfo
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- CN105789699A CN105789699A CN201610173018.0A CN201610173018A CN105789699A CN 105789699 A CN105789699 A CN 105789699A CN 201610173018 A CN201610173018 A CN 201610173018A CN 105789699 A CN105789699 A CN 105789699A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
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Abstract
The invention provides lithium secondary battery electrolyte for preventing the generation of HF (Hydrogen Fluoride) in the electrolyte, a lithium secondary battery prepared from the electrolyte and a preparation method of the lithium secondary battery. The lithium secondary battery electrolyte is prepared from the following components of 95 to 105 parts of solution A, 0.5 to 1.5 parts of ethanolamine and 0.5 to 1.5 parts of hexamethyl disilazane, wherein the solution is 0.8 to 1.2 mol/L of lithium hexafluorophosphate solution; the lithium hexafluorophate solution is prepared from solvent in parts by weight: 45 to 55 parts of ethylene carbonate, 15 to 25 parts of polycarbonate and 25 to 35 parts of diethyl carbonate. The lithium secondary battery electrolyte, the lithium secondary battery and the preparation method of the lithium secondary battery provided by the invention have the beneficial effects that the hexamethyl disilazane and the ethanolamine are added into the electrolyte to serve as stabilizers, so that the condition that water and LiPF6 react to generate the HF is effectively prevented, the stability of the lithium secondary battery electrolyte provided by the invention is improved, and the cycle life of the lithium secondary battery prepared by the preparation method of the lithium secondary battery, provided by the invention, is prolonged.
Description
Technical field
The present invention relates to field of lithium ion battery, specifically lithium secondary battery and preparation method thereof and lithium secondary cell electrolyte.
Background technology
Lithium secondary battery, i.e. chargeable lithium cell.In lithium secondary battery, there are vanadium lithium secondary battery, manganese lithium secondary battery and niobium reason secondary cell.Which kind of is all make negative pole with lithium-aluminium alloy, adopts the battery of organic bath.Lithium secondary battery, is nummular, but the rated voltage of various battery is different.Vanadium lithium secondary battery and manganese lithium secondary battery, rated voltage is 3.0V.The rated voltage of niobium lithium secondary battery is 2.0V.Which kind of lithium secondary battery all has bigger capacity.Self discharge is few, and the ability of anti-over-charging electricity and overdischarge is also strong, and life-time service reliability is high.Using temperature range is-20 DEG C～60 DEG C.This battery, it is possible to charge/discharge about 1000 times repeatedly, power supply supported by the memorizer being mainly used as small communication devices, data communication terminal or the automated office equipments such as mobile phone, Personal Handyphone System, storage card.Vanadium secondary lithium batteries vanadium oxide (V2O5) make positive pole.Except supporting power supply as memorizer, also serve as the remote controller of automobile door lock or the power supply etc. of the remote controller of household electrical appliance.The composite oxides of manganese secondary lithium batteries manganese make positive pole.
Niobium secondary lithium batteries niobium pentaoxide (Nb2O5) make positive pole.Part storage circuit voltage drops to 2.5V from 3.0V, and niobium lithium secondary battery adapts to the needs of these circuit just and develops.Lithium in lithium secondary battery anode exists with the compound form of metal with lithium.But, lithium is also had to exist in the form of an ion, here it is will be detailed below the lithium rechargeable battery mentioned according to lithium existence form in negative pole, it is possible to lithium battery is divided into lithium secondary battery and lithium rechargeable battery.
Plains region, middle and lower reach of Yangtze River air humidity is big so that in injection process, electrolyte can absorb more moisture.And electrolyte itself very easily absorbs water and (all there is the bigger carbonyl of electronegativity and metastable double bond in the structure in solvent of electrolyte, it is easy to polarity H2O forms complexation body or reaction generates corresponding alcohol.Now widely used electrolyte (the LiPF such as 1mol/L6Solution, solvent burden ratio therein is EC50%, PC20%, DEC30%) it is by hexafluorophosphoric acid (LiPF6) it is dissolved in what carbonates mixed solvent was formed, LiPF6Unstable, it is easy to decompose and produce HF.
Following reaction can be there is in electrolyte and water:
H2O+LiPF6→POF3+LiF+2HF
LiPF6→LiF+PF5
H2O+PF5→POF3+2HF
2H2O+PO2F→H3PO4+HF
H2O+(CH2OCOOLi)2→Li2CO3+CO
ROCOOLi+HF→ROCOOH+LiF
Li2CO3+2HF→H2CO3+2LiF
The performance of battery is had a great impact by the Fluohydric acid. more than formed in reaction, and moisture and the acidity of placing a period of time electrolyte all significantly rise, and Fluohydric acid. destroys SEI film, causes two-step film forming, has a strong impact on battery performance.
Summary of the invention
The technical problem to be solved is: provide a kind of lithium secondary cell electrolyte avoiding generating HF in electrolyte and the preparation method of the lithium secondary battery obtained by this electrolyte and lithium secondary battery.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: a kind of lithium secondary cell electrolyte, comprise following component: solution A 95～105 parts, ethanolamine 0.5～1.5 part and HMDS 0.5～1.5 part, described solution is the lithium hexafluorophosphate solution of 0.8～1.2mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 45～55 parts, Merlon 15～25 parts, diethyl carbonate 25～35 parts.
Above-mentioned lithium secondary cell electrolyte, preferably it is made up of solution A 100 parts, ethanolamine 1 part and HMDS 1 part, described solution A is the lithium hexafluorophosphate solution of 1mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 50 parts, Merlon 20 parts, diethyl carbonate 30 parts.
The present invention also provides for a kind of lithium secondary battery including above-mentioned lithium secondary cell electrolyte.
Above-mentioned lithium secondary battery also includes positive plate, negative plate and barrier film, and described positive plate is aluminum foil coating cover, and described negative plate is Copper Foil coated sheet, described barrier film be weave cotton cloth, the one of non-woven fabrics, synthetic resin micro-porous film.
The preparation method that the present invention also provides for a kind of lithium secondary battery, comprises the steps:
Step 1, electrolyte will be injected after intercell evacuation, described electrolyte comprises following component: solution A 95～105 parts, ethanolamine 0.5～1.5 part and HMDS 0.5～1.5 part, described solution is the lithium hexafluorophosphate solution of 0.8～1.2mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 45～55 parts, Merlon 15～25 parts, diethyl carbonate 25～35 parts；
Step 2, pour to the battery after fluid injection helium and means of press seals nail, obtain lithium secondary battery finished product.
The beneficial effects of the present invention is: the stabilizer HMDS in lithium secondary cell electrolyte of the present invention meets water meeting hydrolytic crosslinking, produce methanol, and this material is also dissolved in methanol (methanol is volatile, and evacuation can make it volatilize), the addition of HMDS inhibits LiPF6With H2O, free acid etc. react, and stop the formation of HF in electrolyte, improve the stability of electrolyte, improve the cycle performance of battery；Ethanolamine then improves electrolyte stability and extends cycle life of lithium ion battery, adds quantitative ethanolamine in the electrolytic solution, does not affect the compatibility of electrolyte and positive and negative electrode, and can suppress LiPF in electrolyte6Hydrolysis and pyrolytic reaction, make battery capacity attenuation rate reduce by 50%, improve the stability of electrolyte and the cycle life of battery；HMDS and ethanolamine combine and use, and effectively prevent water and LiPF6Reaction generates HF, improves the stability of lithium secondary cell electrolyte of the present invention, extends the cycle life of the lithium secondary battery that the preparation method of lithium secondary battery of the present invention obtains.
Detailed description of the invention
By describing the technology contents of the present invention in detail, being realized purpose and effect, it is explained below in conjunction with embodiment.
The design of most critical of the present invention is in that: add HMDS and ethanolamine in the electrolytic solution as stabilizer, can avoid generation HF in electrolyte, water and acid are played Stabilization.
The present invention provides a kind of lithium secondary cell electrolyte, comprise following component: solution A 95～105 parts, ethanolamine 0.5～1.5 part and HMDS 0.5～1.5 part, described solution is the lithium hexafluorophosphate solution of 0.8～1.2mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 45～55 parts, Merlon 15～25 parts, diethyl carbonate 25～35 parts.
Above-mentioned lithium secondary cell electrolyte, preferably it is made up of solution A 100 parts, ethanolamine 1 part and HMDS 1 part, described solution A is the lithium hexafluorophosphate solution of 1mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 50 parts, Merlon 20 parts, diethyl carbonate 30 parts.
The present invention also provides for a kind of lithium secondary battery including above-mentioned lithium secondary cell electrolyte.
Above-mentioned lithium secondary battery also includes positive plate, negative plate and barrier film, and described positive plate is aluminum foil coating cover, and described negative plate is Copper Foil coated sheet, described barrier film be weave cotton cloth, the one of non-woven fabrics, synthetic resin micro-porous film.
The preparation method that the present invention also provides for a kind of lithium secondary battery, comprises the steps:
Step 1, electrolyte will be injected after intercell evacuation, described electrolyte comprises following component: solution A 95～105 parts, ethanolamine 0.5～1.5 part and HMDS 0.5～1.5 part, described solution is the lithium hexafluorophosphate solution of 0.8～1.2mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 45～55 parts, Merlon 15～25 parts, diethyl carbonate 25～35 parts；
Step 2, pour to the battery after fluid injection helium and means of press seals nail, obtain lithium secondary battery finished product.
Stabilizer HMDS added by electrolyte of the present invention is organic amine material, HMDS (HMDS) meets water meeting hydrolytic crosslinking, produce methanol, and this material is also dissolved in methanol, and (methanol is volatile, evacuation can make it volatilize), the addition of HMDS inhibits LiPF6With H2O, free acid etc. react, and stop the formation of HF in electrolyte, improve the stability of electrolyte, improve the cycle performance of battery.
Ethanolamine in lithium secondary cell electrolyte of the present invention then improves electrolyte stability and extends cycle life of lithium ion battery, adds quantitative ethanolamine in the electrolytic solution, does not affect the compatibility of electrolyte and positive and negative electrode, and can suppress LiPF in electrolyte6Hydrolysis and pyrolytic reaction, make battery capacity attenuation rate reduce by 50%, improve the stability of electrolyte and the cycle life of battery；Both the above material can combine and effectively prevent water and LiPF6Reaction generates HF, improves the stability of electrolyte, extends the cycle life of battery.
Embodiment 1
A kind of lithium secondary cell electrolyte, comprise following component: solution A 95～105 parts, ethanolamine 0.5～1.5 part and HMDS 0.5～1.5 part, described solution is the lithium hexafluorophosphate solution of 0.8～1.2mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 45～55 parts, Merlon 15～25 parts, diethyl carbonate 25～35 parts.
Embodiment 2
A kind of lithium secondary cell electrolyte, comprise following component: solution A 100 parts, ethanolamine 1 part and HMDS 1 part composition, described solution A is the lithium hexafluorophosphate solution of 1mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 50 parts, Merlon 20 parts, diethyl carbonate 30 parts.
Embodiment 3
A kind of lithium secondary battery, including the lithium secondary cell electrolyte in positive plate, negative plate, barrier film and embodiment 1, described positive plate is aluminum foil coating cover, and described negative plate is Copper Foil coated sheet, and described barrier film is synthetic resin micro-porous film.
Embodiment 4
The preparation method of a kind of lithium secondary battery, comprises the steps:
Step 1, the electrolyte that will inject after intercell evacuation in embodiment 1；
Step 2, pour to the battery after fluid injection helium and means of press seals nail, obtain lithium secondary battery finished product.
In sum, provided by the invention have the beneficial effects that: the stabilizer HMDS in lithium secondary cell electrolyte of the present invention meets water can hydrolytic crosslinking, produce methanol, and this material is also dissolved in methanol, and (methanol is volatile, evacuation can make it volatilize), the addition of HMDS inhibits LiPF6With H2O, free acid etc. react, and stop the formation of HF in electrolyte, improve the stability of electrolyte, improve the cycle performance of battery；Ethanolamine then improves electrolyte stability and extends cycle life of lithium ion battery, adds quantitative ethanolamine in the electrolytic solution, does not affect the compatibility of electrolyte and positive and negative electrode, and can suppress LiPF in electrolyte6Hydrolysis and pyrolytic reaction, make battery capacity attenuation rate reduce by 50%, improve the stability of electrolyte and the cycle life of battery；HMDS and ethanolamine combine and use, and effectively prevent water and LiPF6Reaction generates HF, improves the stability of lithium secondary cell electrolyte of the present invention, extends the cycle life of the lithium secondary battery that the preparation method of lithium secondary battery of the present invention obtains.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalents utilizing description of the present invention to make, or directly or indirectly it is used in relevant technical field, all in like manner include in the scope of patent protection of the present invention.
Claims (5)
1. a lithium secondary cell electrolyte, it is characterized in that, comprise following component: solution A 95～105 parts, ethanolamine 0.5～1.5 part and HMDS 0.5～1.5 part, described solution is the lithium hexafluorophosphate solution of 0.8～1.2mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 45～55 parts, Merlon 15～25 parts, diethyl carbonate 25～35 parts.
2. lithium secondary cell electrolyte according to claim 1, it is characterized in that: solution A 100 parts, ethanolamine 1 part and HMDS 1 part, described solution A is the lithium hexafluorophosphate solution of 1mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 50 parts, Merlon 20 parts, diethyl carbonate 30 parts.
3. a lithium secondary battery, it is characterised in that include the lithium secondary cell electrolyte described in any one of claim 1～2.
4. lithium secondary battery according to claim 3, it is characterized in that: also include positive plate, negative plate and barrier film, described positive plate is aluminum foil coating cover, and described negative plate is Copper Foil coated sheet, described barrier film be weave cotton cloth, the one of non-woven fabrics, synthetic resin micro-porous film.
5. the preparation method of lithium secondary battery, it is characterised in that comprise the steps:
Step 1, electrolyte will be injected after intercell evacuation, described electrolyte comprises following component: solution A 95～105 parts, ethanolamine 0.5～1.5 part and HMDS 0.5～1.5 part, described solution is the lithium hexafluorophosphate solution of 0.8～1.2mol/L, described lithium hexafluorophosphate solution includes the solvent of following weight portion: ethylene carbonate 45～55 parts, Merlon 15～25 parts, diethyl carbonate 25～35 parts；
Step 2, pour to the battery after fluid injection helium and means of press seals nail, obtain lithium secondary battery finished product.
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| CN201610173018.0A CN105789699A (en) | 2016-03-22 | 2016-03-22 | Lithium secondary battery and preparation method thereof as well as lithium secondary battery electrolyte |
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| CN201610173018.0A CN105789699A (en) | 2016-03-22 | 2016-03-22 | Lithium secondary battery and preparation method thereof as well as lithium secondary battery electrolyte |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055574A (en) * | 2017-04-10 | 2017-08-18 | 多氟多化工股份有限公司 | A kind of method of purification of lithium hexafluoro phosphate |
| CN107749488A (en) * | 2016-11-28 | 2018-03-02 | 万向二三股份公司 | A kind of lithium battery of water system positive pole and preparation method thereof |
| CN108878978A (en) * | 2018-06-29 | 2018-11-23 | 桑顿新能源科技有限公司 | A kind of anti-overcharge lithium battery electrolytes containing silicone additives |
| CN111244542A (en) * | 2020-03-21 | 2020-06-05 | 湖州安和材料科技有限公司 | Low-temperature-resistant lithium battery electrolyte and preparation process thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749488A (en) * | 2016-11-28 | 2018-03-02 | 万向二三股份公司 | A kind of lithium battery of water system positive pole and preparation method thereof |
| CN107055574A (en) * | 2017-04-10 | 2017-08-18 | 多氟多化工股份有限公司 | A kind of method of purification of lithium hexafluoro phosphate |
| CN108878978A (en) * | 2018-06-29 | 2018-11-23 | 桑顿新能源科技有限公司 | A kind of anti-overcharge lithium battery electrolytes containing silicone additives |
| CN108878978B (en) * | 2018-06-29 | 2021-11-05 | 桑顿新能源科技(长沙)有限公司 | Organic silicon additive-containing overcharge-preventing lithium battery electrolyte |
| CN111244542A (en) * | 2020-03-21 | 2020-06-05 | 湖州安和材料科技有限公司 | Low-temperature-resistant lithium battery electrolyte and preparation process thereof |
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Application publication date: 20160720 |