CN101752610A - Non-aqueous electrolyte lithium metal battery and preparation method thereof - Google Patents
Non-aqueous electrolyte lithium metal battery and preparation method thereof Download PDFInfo
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- CN101752610A CN101752610A CN200810154215A CN200810154215A CN101752610A CN 101752610 A CN101752610 A CN 101752610A CN 200810154215 A CN200810154215 A CN 200810154215A CN 200810154215 A CN200810154215 A CN 200810154215A CN 101752610 A CN101752610 A CN 101752610A
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- lithium
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a non-aqueous electrolyte lithium metal battery and a preparation method thereof, which belong to the technical field of lithium batteries. The non-aqueous electrolyte lithium metal battery comprises an anode, a cathode and non-aqueous electrolyte, and is characterized in that the cathode is made of foil metal which does not form alloy with lithium and the anode is made of lithium-embedded active material. The preparation method for the non-aqueous electrolyte lithium metal battery comprises the following steps: fixing the clean foil metal which does not form the alloy with the lithium by a clamp or coiling the clean foil metal to form coils, and preparing a LiPON lithium-ion solid electrolyte protective film in the nitrogen plasma atmosphere by adopting a magnetron sputtering method; coiling or laminating the metal foil with the LiPON film on the surface, the anode material of the lithium ion battery and a diaphragm to form a battery core; injecting the non-aqueous electrolyte solution into the battery core; and charging the battery core to form the non-aqueous electrolyte lithium metal battery. The non-aqueous electrolyte lithium metal battery has the advantages of simple structure, convenient storage, high specific energy, reasonable process, high safety, high lithium utilization efficiency and good cycle performance.
Description
Technical field
The invention belongs to technical field of lithium batteries, particularly relate to a kind of non-aqueous electrolyte lithium metal battery and preparation method thereof.
Background technology
At present, lithium metal has the highest specific capacity (3.85Ah/g) and electronegative potential, and becomes the negative material of high-energy battery, simultaneously, adopts the lithium primary cell of lithium anode can be widely used in digital product and electronic toy and communication apparatus and national defence field; Lithium metal secondary battery then is the high-energy battery of new generation after lithium ion battery.General lithium primary cell and lithium metal secondary battery all adopt metallic lithium foil to make negative active core-shell material, be compressed on nickel screen, copper mesh or the Copper Foil, and capacity are in excess in positive electrode usually greatly, and its excess quantity reaches more than 3 times usually.Cause the specific energy of traditional lithium series battery lower like this, simultaneously owing to the excessive more fail safe that influences of lithium.Positive electrode as lithium primary cell adopts manganese dioxide, ferrous sulfide, sulfur dioxide, thionyl chloride etc. usually, does not promptly contain lithium, and such battery can directly discharge; The positive electrode employing cobalt acid lithium of lithium ion battery etc. has the transition metal oxide of layer structure, and spinel lithium manganate or olivine LiFePO4 etc., and its lithium source of such lithium ion anode material is at positive pole.
Summary of the invention
The technical problem of the present invention for existing in the solution known technology, and a kind of non-aqueous electrolyte lithium metal battery and preparation method thereof is provided.
One of purpose of the present invention provide a kind of simple in structure, safe, be convenient to store, the non-aqueous electrolyte lithium metal battery of high-energy-density.
The technical scheme that the invention of this non-aqueous electrolyte lithium metal battery is taked is:
A kind of non-aqueous electrolyte lithium metal battery comprises positive pole, negative pole and nonaqueous electrolyte, is characterized in: negative pole is the metal forming that does not form alloy with lithium, and positive pole has embedding lithium active material.
Non-aqueous electrolyte lithium metal battery of the present invention can also adopt following technical measures:
Described non-aqueous electrolyte lithium metal battery is characterized in: negative terminal surface has the lithium ion solid electrolyte film.
Described non-aqueous electrolyte lithium metal battery is characterized in: solid electrolyte film is glassy state LiPON.
Described non-aqueous electrolyte lithium metal battery, be characterized in: embedding lithium active material is cobalt nickel oxide manganses lithium, nickel cobalt lithium oxide, the cobalt-lithium oxide with layer structure, have manganese oxide lithium, the nickel oxide manganese lithium of spinel structure or have LiFePO4 of olivine structural etc., and the mixture of above-mentioned lithiated intercalation compound or derivative.
Described non-aqueous electrolyte lithium metal battery is characterized in: metal forming is Copper Foil, nickel foil, titanium foil or stainless steel foil.
Two of purpose of the present invention provides that a kind of technical process is simple, safe, the preparation method of the non-aqueous electrolyte lithium metal battery of lithium utilance height, good cycle.
The technical scheme that the preparation method of non-aqueous electrolyte lithium metal battery of the present invention takes is:
The preparation method of non-aqueous electrolyte lithium metal battery is characterized in that: the preparation method may further comprise the steps:
Step 1: the metal forming of cleaning is fixed or coiling with anchor clamps, in the nitrogen plasma atmosphere, adopt magnetron sputtering method to prepare LiPON lithium ion solid electrolyte diaphragm;
Step 2: the surface have the metal forming of LiPON film and anode material for lithium-ion batteries and membrane coil around or lamination make electric core;
Step 3: inject non-aqueous electrolytic solution;
Step 4: charge, form non-aqueous electrolyte lithium metal battery.
The preparation method of non-aqueous electrolyte lithium metal battery of the present invention can also adopt following technical measures:
The preparation method of described non-aqueous electrolyte lithium metal battery is characterized in: after charging, repeated charge promptly obtains the non-aqueous electrolyte lithium metal secondary cell again.
Advantage that the present invention has and good effect:
Non-aqueous electrolyte lithium metal battery and preparation method thereof adopts brand-new technology scheme of the present invention, and the metal forming of employing lithium inertia etc. are as negative pole, and positive pole adopts the embedded positive electrode of lithium ion.Combinations thereof constitutes a kind of discharge attitude lithium battery, and is as safe as a house and it is convenient to long term storage, when needing work, charges earlier on negative pole-the electro-deposition lithium, and has activity.The negative pole lithium of such lithium metal battery is fully from positive pole, and lithium is excessive and can have the specific energy higher than traditional lithium battery.Constitute lithium secondary battery when it uses repeatedly simultaneously.And further proposed the negative pole of lithium ion solid electrolyte film protection among the present invention again and when making its electro-deposition lithium, more be not easy to form Li dendrite, thereby improve the utilization ratio and the cycle performance of fail safe, lithium.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, exemplify following examples now, be described in detail as follows:
Present embodiment has exemplified LiNi
1/3Co
1/3Mn
1/3O
2/ Cu combination, electrolyte is the LiPF of 1.0mol/L
6/ EC+DEC+DMC (volume ratio 1: 1: 1).But the present invention is not limited only to this, and positive pole can be the mixture or the derivative of other lithium ion insert materials such as cobalt-lithium oxide, galaxite, LiFePO4 and above-mentioned lithiated intercalation compound; Negative pole can be nickel foil, titanium foil and stainless steel foil etc.; Electrolyte can be the organic electrolyte of other electrolytic salt, solvent, also can be other nonaqueous electrolytes such as polymer dielectric and ionic liquid.
Embodiment 1
Non-aqueous electrolyte lithium metal battery comprises positive pole, negative pole and nonaqueous electrolyte, and its negative pole is the Copper Foil that does not form alloy with lithium, and copper foil surface has glassy state LiPON solid electrolyte film.Positive pole has embedding lithium active material cobalt nickel oxide manganses lithium.
Embodiment 2
The preparation method of non-aqueous electrolyte lithium metal battery may further comprise the steps:
At first copper foil surface is cleaned up successively drying with ethanol and acetone;
Step 1: Copper Foil is fixed on the sample stage with anchor clamps, in the nitrogen plasma atmosphere, adopts magnetron sputtering method to prepare LiPON lithium ion solid electrolyte diaphragm;
Step 2: the surface have the metal forming of LiPON film and anode material for lithium-ion batteries and membrane coil around or lamination make electric core;
Step 3: inject non-aqueous electrolytic solution;
Step 4: charge, form non-aqueous electrolyte lithium metal battery.Repeated charge promptly obtains the non-aqueous electrolyte lithium metal secondary cell again.
Operation control and preparation process that present embodiment is concrete:
1.LiPON the preparation of film protection negative pole
With Copper Foil ultrasonic washing 5 minutes in ethanolic solution, use the acetone rinsing again, air dry.It is fixing then Copper Foil to be put into the rf magnetron sputtering platform, under the 0.5Pa condition, adopts the Li of compacting sintering at nitrogen partial pressure
3PO
4Target is 2W/cm at target power output
2Carry out sputter 16 hours under the condition, form the Copper Foil that thickness is about the LiPON film protection of 300nm.Be cut into the electrode for cell of 10cmX8cm (side leaves the position of 1cmX0.5cm soldering polar ear), the print of going out diameter 2cm simultaneously is for test.The fine and close free of pinholes of LiPON film.This print and barrier film and lithium are dressed up 2430 type button cells to electrode, and the lithium of first electro-deposition 10mAh discharges and recharges test with the 1mA electric current then, and its cycle efficieny is more than 98%, and is highly stable.
2. Zheng Ji preparation
Take by weighing LiNi
1/3Co
1/3Mn
1/3O
2(ternary) positive electrode active materials, adhesive and conductive agent, by the N-methyl-2-of the positive electrode active materials mixture of 92wt%, polyvinylidene fluoride (PVdF) bonding agent than pyrrolidone (NMP) solution and to make the content of PVdF be 5wt%, 3wt% acetylene black as electric conducting material, mix and form cathode mix, in mixture, add NMP and prepare pastel with mixer, then this pastel being coated onto equably thickness is on the 20 μ m aluminium foils, again drying, roll-in and make positive plate.Coating weight is 42mg/cm
2The pole piece that is cut into area and is 9.8cmX7.8cm is standby.
3. cell preparation
Be assembled into test battery, vacuum decompression injection electrolyte (the 1mol/L LiPF that contains 1%VC with anodal 6 with 25 microns microporous polyethylene barrier film, above-mentioned 17 of lithium electrodes
6EC+DEC+DMC (1: 1: 1) solution) make flexible-packed battery, seal back power supply test chemical.
4. charge-discharge test:
Charging is carried out under 0.1 multiplying power, charges to the 4.3V constant voltage 2 hours, then with the 0.2C multiplying power discharging to 2.5V.Calculate discharge capacity and energy density.The results are shown in Table 1.
5. internal resistance rate of change:
Battery after the full charging is with the rate of change (1kHz) of the strong alternating current impedance instrument test of Su Li internal resistance and be recorded in the table 1.Wherein impedance rate of change is compared with initial impedance with the impedance after placing, and writes down all rates of change, the mean value around getting.
Impedance rate of change=(Z-Z
0)/Z
0* 100, Z is the impedance after placing, Z in the formula
0Be initial impedance.
Embodiment 3
Negative material only adopts Copper Foil, no LiPON film, and all the other are identical with embodiment 2, and discharge capacity and energy density are recorded in the table 1.
Comparative Examples 1
Negative pole is compressed on the copper mesh both sides as negative pole with 50 micron metal lithium paper tinsels, and all the other are identical with embodiment 2, repeats above test, and outcome record is in table 1.
| Project | Negative pole | Battery capacity (Ah) | Specific energy (Wh/kg) | Stabilization efficiency (%) | Stability (internal resistance week rate of change %) |
| Embodiment 2 | ??LiPON/Cu | ??3.3 | ??285 | ??99.6 | ??2.2％ |
| Project | Negative pole | Battery capacity (Ah) | Specific energy (Wh/kg) | Stabilization efficiency (%) | Stability (internal resistance week rate of change %) |
| Embodiment 3 | ??Cu | ??3.1 | ??260 | ??95.5 | ??21.3％ |
| Comparative Examples 1 | The Li paper tinsel | ??3.2 | ??213 | ??94.8 | ??120％ |
From above result as can be known: adopt the specific energy of the lithium battery of Copper Foil or LiPON protection negative pole to be higher than traditional lithium battery far away.Discharge and recharge stabilization efficiency and be the battery of battery＞Li paper tinsel of battery＞Cu of LiPON/Cu in proper order, and the battery of the good stability of LiPON/Cu battery and traditional lithium paper tinsel negative pole.And LiPON/Cu is best at raising specific energy, stabilizing effect.
Claims (7)
1. a non-aqueous electrolyte lithium metal battery comprises positive pole, negative pole and nonaqueous electrolyte, it is characterized in that: negative pole is the metal forming that does not form alloy with lithium, and positive pole has embedding lithium active material.
2. non-aqueous electrolyte lithium metal battery according to claim 1 is characterized in that: negative terminal surface has the lithium ion solid electrolyte film.
3. non-aqueous electrolyte lithium metal battery according to claim 2 is characterized in that: solid electrolyte film is glassy state LiPON.
4. non-aqueous electrolyte lithium metal battery according to claim 1, it is characterized in that: embedding lithium active material is cobalt nickel oxide manganses lithium, nickel cobalt lithium oxide, the cobalt-lithium oxide with layer structure, have manganese oxide lithium, the nickel oxide manganese lithium of spinel structure or have the LiFePO4 of olivine structural, and the mixture of above-mentioned lithiated intercalation compound or derivative.
5. non-aqueous electrolyte lithium metal battery according to claim 1 is characterized in that: metal forming is Copper Foil, nickel foil, titanium foil or stainless steel foil.
6. the preparation method of non-aqueous electrolyte lithium metal battery according to claim 1, it is characterized in that: the preparation method may further comprise the steps:
Step 1: the metal forming of cleaning is fixed or coiling with anchor clamps, in the nitrogen plasma atmosphere, adopt magnetron sputtering method to prepare LiPON lithium ion solid electrolyte diaphragm;
Step 2: surface metal forming that has a LiPON film and the positive pole that contains embedding lithium active material and membrane coil around or lamination make electric core;
Step 3: inject non-aqueous electrolytic solution;
Step 4: charge, form non-aqueous electrolyte lithium metal battery.
7. the preparation method of non-aqueous electrolyte lithium metal battery according to claim 6, it is characterized in that: after charging, repeated charge promptly obtains the non-aqueous electrolyte lithium metal secondary cell again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200810154215A CN101752610A (en) | 2008-12-18 | 2008-12-18 | Non-aqueous electrolyte lithium metal battery and preparation method thereof |
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|---|---|---|---|
| CN200810154215A CN101752610A (en) | 2008-12-18 | 2008-12-18 | Non-aqueous electrolyte lithium metal battery and preparation method thereof |
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| CN101752610A true CN101752610A (en) | 2010-06-23 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102629675A (en) * | 2012-04-25 | 2012-08-08 | 苏州大学 | Method for improving diaphragm property of secondary battery, diaphragm of secondary battery and secondary battery |
| CN105575678A (en) * | 2015-12-17 | 2016-05-11 | 中国电子科技集团公司第十八研究所 | Preparation method of electrode membrane used for Li-ion capacitor |
| CN106803580A (en) * | 2017-01-19 | 2017-06-06 | 浙江大学 | A kind of negative material for lithium metal battery |
| CN107275670A (en) * | 2017-07-06 | 2017-10-20 | 钟旭航 | The preparation method of lithium-ion-power cell and preparation method thereof, its barrier film and barrier film, and for forming the slurry of barrier film |
| CN108417773A (en) * | 2018-02-05 | 2018-08-17 | 山东丰元化学股份有限公司 | A kind of LiFePO4 combination electrode and its preparation method and application |
| CN110915036A (en) * | 2017-07-28 | 2020-03-24 | 罗伯特·博世有限公司 | Battery pack with single ion conductive layer |
| WO2020259480A1 (en) * | 2019-06-27 | 2020-12-30 | Li-Fun Technology Co., Ltd | Lithium primary battery |
| CN112531173A (en) * | 2019-09-17 | 2021-03-19 | 宁德新能源科技有限公司 | Metal foil treatment process, electrode plate and electrochemical device |
-
2008
- 2008-12-18 CN CN200810154215A patent/CN101752610A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102629675A (en) * | 2012-04-25 | 2012-08-08 | 苏州大学 | Method for improving diaphragm property of secondary battery, diaphragm of secondary battery and secondary battery |
| CN105575678A (en) * | 2015-12-17 | 2016-05-11 | 中国电子科技集团公司第十八研究所 | Preparation method of electrode membrane used for Li-ion capacitor |
| CN106803580A (en) * | 2017-01-19 | 2017-06-06 | 浙江大学 | A kind of negative material for lithium metal battery |
| CN107275670A (en) * | 2017-07-06 | 2017-10-20 | 钟旭航 | The preparation method of lithium-ion-power cell and preparation method thereof, its barrier film and barrier film, and for forming the slurry of barrier film |
| WO2019007225A1 (en) * | 2017-07-06 | 2019-01-10 | 钟旭航 | Lithium ion power battery and manufacturing method therefor, a diaphragm and a manufacturing method therefor, and slurry for forming diaphragm |
| CN110915036A (en) * | 2017-07-28 | 2020-03-24 | 罗伯特·博世有限公司 | Battery pack with single ion conductive layer |
| CN108417773A (en) * | 2018-02-05 | 2018-08-17 | 山东丰元化学股份有限公司 | A kind of LiFePO4 combination electrode and its preparation method and application |
| WO2020259480A1 (en) * | 2019-06-27 | 2020-12-30 | Li-Fun Technology Co., Ltd | Lithium primary battery |
| CN112531173A (en) * | 2019-09-17 | 2021-03-19 | 宁德新能源科技有限公司 | Metal foil treatment process, electrode plate and electrochemical device |
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Open date: 20100623 |