CN105098189A - Anode material additive and preparation method thereof - Google Patents
Anode material additive and preparation method thereof Download PDFInfo
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- CN105098189A CN105098189A CN201410216684.9A CN201410216684A CN105098189A CN 105098189 A CN105098189 A CN 105098189A CN 201410216684 A CN201410216684 A CN 201410216684A CN 105098189 A CN105098189 A CN 105098189A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides an anode material additive and a preparation method thereof. The anode material additive is lithium of which the surface is coated with a lithium phosphate cladding layer. The lithium phosphate cladding lithium material prepared according to the invention serves as the anode material additive, and thus, the problem of low initial charging and discharging efficiency of a lithium ion battery is effectively solved.
Description
Technical field
The present invention relates to a kind of negative material additive and preparation method thereof.
Background technology
Lithium ion battery due to its have that voltage is high, the advantage such as energy density is large, long service life, pollution-free and self discharge are little, be widely used in portable electric appts and electric automobile.At present, the negative material of commercial li-ion battery is mainly graphite cathode material, and its theoretical capacity is 372mAh/g, and actual development is close to theoretical capacity, can development space limited, can not adapt to the demand of electric automobile to high-capacity high-power lithium ion battery.
Some novel negative materials can have very high theoretical capacity, and the theoretical capacity of such as silicon is 4200mAh/g, but its first charge-discharge efficiency is all lower.When these negative materials and positive electrode are matched to battery, a large amount of lithium ions is just consumed and cannot gets back to positive pole after first time charging.The object of original employing Large Copacity negative pole is exactly the population size increasing battery, but the low actual capacity that seriously can reduce lithium battery on the contrary of first charge-discharge efficiency, limit its application.
In lithium battery, the loss of irreversible capacity first directly causes the loss of the energy content of battery.In fact capacitance loss is exactly the loss of lithium, and such as efficiency is 75% first, then after first time charging, the lithium of 25% just irreversibly consumes.Loss mainly comes from the following aspects: the 1) fault of construction of positive pole, lithium ion can not depart from smoothly positive pole lattice structure or depart from after reversibly do not embed; 2) fault of construction of negative pole, is embedded into the part lithium ion not reversibly deintercalation of negative pole during charging; 3) part lithium ion reacts at negative pole and positive electrode surface and electrolyte and defines SEI film.Generally, lithium all comes from positive electrode, composition the most expensive in this lithium battery.In cathode pole piece, add lithium more than needed, be the directly the most cheap mode addressed this problem.But lithium metal is very unstable in atmosphere, causes impassable obstacle to actual production.
At present, low having become of first charge-discharge efficiency hinders many negative materials, and especially jumbo negative material realizes the technical bottleneck of commercial applications.So, fundamentally solve the low problem of lithium battery first charge-discharge efficiency in the urgent need to developing a kind of effective and practical technology.
Summary of the invention
The invention provides a kind of additive for lithium ion battery negative material, this additive application can improve first charge-discharge efficiency effectively in lithium ion battery.
According to object of the present invention, negative material additive of the present invention is the lithium that Surface coating has lithium phosphate coating layer.
According to one embodiment of the present invention, the thickness of above-mentioned lithium phosphate coating layer is 1nm ~ 10 μm, and the thickness of preferably phosphoric acid lithium coating layer is 50nm ~ 1 μm.
Another object of the present invention is, a kind of preparation method of above-mentioned negative material additive is provided, comprise: a kind of organic solvent is provided, respectively lithium powder and pure phosphoric acid are added in described organic solvent and react, uniform stirring, by removal of solvents after having reacted, obtain the lithium that Surface coating has lithium phosphate coating layer.
According to the embodiment of the present invention, at least one in the alkane that above-mentioned organic solvent is selected from ether, carbon number is 7-20, aromatic hydrocarbons, sulfone class organic solvent etc.Preferably, above-mentioned organic solvent is ether; More preferably, above-mentioned organic solvent is oxolane.According to another embodiment of the invention, above-mentioned organic solvent is sulfolane.
According to the embodiment of the present invention, the particle diameter of above-mentioned lithium powder is 10nm ~ 100 μm, and the particle diameter of preferred lithium powder is 0.5 ~ 10 μm.
According to the embodiment of the present invention, wherein, the thickness of lithium phosphate coating layer is 1nm ~ 10 μm, and the thickness of preferably phosphoric acid lithium coating layer is 50nm ~ 1 μm.The thickness of lithium phosphate coating layer can be controlled by the amount of the pure phosphoric acid added.In order to reach object of the present invention, above-mentioned pure phosphoric acid is 1:100 ~ 1:5 with the mole ratio of lithium, and preferred pure phosphoric acid is 1:60 ~ 1:9 with the mole ratio of lithium.
According to the embodiment of the present invention, above-mentioned pure phosphoric acid can be adopted and prepare with the following method: in deionized water or phosphoric acid solution (such as concentration is the phosphoric acid solution of 85%), add enough phosphorus pentoxides, heat at 60 ~ 100 DEG C (such as 80 DEG C), make water and phosphorus pentoxide complete reaction, obtain pure phosphoric acid.
In the present invention, the addition sequence of pure phosphoric acid and lithium powder is also unrestricted.First can configure the organic solution of pure phosphoric acid, and then add lithium powder; Also first lithium powder can be joined in organic solvent, more slowly add pure phosphoric acid.In order to be that the lithium phosphate coating layer that obtains is more even, and add fast response and carry out, preferably under stirring, add pure phosphoric acid or lithium powder.
Another object of the present invention is, provides a kind of lithium ion battery, and the negative pole of this lithium ion battery includes negative material and negative material additive, and described negative material additive is the lithium powder that Surface coating has lithium phosphate coating layer.
According to one embodiment of the present invention, the preferred jumbo negative material of above-mentioned negative material, described negative material can be selected from least one in graphite, silicon, tin, Graphene, carbon nano-tube, lithium titanate etc.
In order to solve problems of the prior art, the present invention is at the Li of lithium metal outer wrap densification
3pO
4coating layer, this coating layer can moisture in blocks air to the invasion and attack of lithium metal, make lithium powder can be mixed into cathode pole piece in normal conditions, and prepare lithium battery in normal conditions.Obtain the coated lithium material of lithium phosphate by the present invention, as negative material additive, efficiently solve the problem that lithium ion battery first charge-discharge efficiency is low.
Accompanying drawing explanation
Fig. 1: the coated lithium material XRD spectra of lithium phosphate of preparation in embodiment 1;
Fig. 2: the button electrical test results (specific capacity) prepared in embodiment 1 and comparative example 1;
Fig. 3: the button electrical test results (pressing in electric discharge) prepared in embodiment 1 and comparative example 1;
Fig. 4: in embodiment 1, the coated lithium material SEM of lithium phosphate of preparation schemes;
Fig. 5: the cell testing results of preparation in embodiment 2, embodiment 3 and comparative example 2.
Embodiment
Following specific embodiment is to invention has been detailed description, but the present invention is not restricted to following examples.
Prepared by pure phosphoric acid: add enough phosphorus pentoxides in the phosphoric acid solution of 85%, 80 DEG C of heating, make water and phosphorus pentoxide complete reaction, obtain pure phosphoric acid.
Operation sequence: be solvent with tetrahydrofuran solution, floods appropriate lithium; Add pure phosphoric acid gradually again, agitating solution between the stage of reaction.
Embodiment 1:
In glove box, prepare the tetrahydrofuran solution that pure phosphoric acid concentration is 10% (phosphoric acid 0.28g, oxolane 2.5g), stir, slowly add the lithium sheet that 0.06g pulverizes, agitating solution, treats that oxolane volatilizees completely, obtains the coated lithium material of lithium phosphate.
Coated for the lithium phosphate of above-mentioned preparation lithium material is carried out XRD analysis, result as shown in Figure 1: have Li in spectrogram
3pO
4the existence of characteristic peak, proves that there is Li on lithium surface
3pO
4coating layer generates.
Button electricity preparation: prepare slurry according to the ratio of nickel-cobalt lithium manganate cathode material (NCM)/conductive agent/PVDF=8:1:1, through coating, dry and the obtained anode pole piece of section, cathode pole piece is the pole piece adopting the coated lithium material of lithium phosphate of above-mentioned preparation to be pressed into, electrolyte adopts il electrolyte, above-mentioned anode pole piece, cathode pole piece and electrolyte is assembled into button cell and carries out electrochemical property test.
Comparative example 1:
Except cathode pole piece be adopt the lithium sheet of not coated lithium powder compacting except, other all adopts the materials and process identical with embodiment 1 to prepare button cell.
Electrical test results is detained as shown in Figures 2 and 3 in embodiment 1 and comparative example 1.Wherein lithium powder sheet is Li
3pO
4coated lithium material compacting forms, and shows closely similar with the lithium sheet of not coated mistake in NCM half-cell.Li is described
3pO
4do not affect the electrochemical effect of lithium sheet.
Fig. 4 is that the coated lithium material SEM of lithium phosphate of preparation in embodiment 1 schemes, and as can be seen from the figure, defines structural integrity and continuous print coating layer on the surface of lithium powder, in conjunction with the test result of XRD, can prove that this coating layer is lithium phosphate.
From the above results, the lithium metal of coated mistake, equally can play the effect the same with not coated lithium metal, i.e. the coated stability adding lithium metal, and does not damage its electrochemical properties.
Embodiment 2:
With nickle cobalt lithium manganate (NCM) for positive electrode, porous silicon is negative material, wherein be added with the coated lithium material of lithium phosphate (prepared by embodiment 1) of 10wt%, lithium hexafluoro phosphate carbonic ester electrolyte and PVDF barrier film is adopted to be assembled into battery, to the test result of its specific discharge capacity and coulombic efficiency as shown in Figure 5.
Embodiment 3:
With nickle cobalt lithium manganate (NCM) for positive electrode, porous silicon is negative material, wherein be added with the coated lithium material of lithium phosphate (prepared by embodiment 1) of 20wt%, lithium hexafluoro phosphate carbonic ester electrolyte and PVDF barrier film is adopted to be assembled into battery, to the test result of its specific discharge capacity and coulombic efficiency as shown in Figure 5.
Comparative example 2:
With nickle cobalt lithium manganate (NCM) for positive electrode, porous silicon is negative material, adopts lithium hexafluoro phosphate carbonic ester electrolyte and PVDF barrier film to be assembled into battery, to the test result of its specific discharge capacity and coulombic efficiency as shown in Figure 5.
Test condition:
First time discharge and recharge: first carry out being charged to 4.3V with 0.1C multiplying power, be then less than 0.01mA complete charge at 4.3V constant voltage charge to electric current; Then discharge with 0.1C, cut-ff voltage 2.5V;
Second time discharge and recharge: first carry out being charged to 4.3V with 0.2C multiplying power, be then less than 0.01mA complete charge at 4.3V constant voltage charge to electric current; Then discharge with 0.2C, cut-ff voltage 2.5V;
Third time discharge and recharge: first carry out being charged to 4.3V with 0.2C multiplying power, be then less than 0.01mA complete charge at 4.3V constant voltage charge to electric current; Then discharge with 1.0C, cut-ff voltage 2.5V;
4th discharge and recharge: first carry out being charged to 4.3V with 0.2C multiplying power, be then less than 0.01mA complete charge at 4.3V constant voltage charge to electric current; Then discharge with 5.0C, cut-ff voltage 2.5V;
5th time and discharge and recharge later: first carry out being charged to 4.3V with 1.0C multiplying power, be then less than 0.01mA complete charge at 4.3V constant voltage charge to electric current; Then discharge with 1.0C, cut-ff voltage 2.5V.
Embodiment 2, embodiment 3 and the difference of comparative example 2 are only that the amount whether being added with the coated lithium material of lithium phosphate and interpolation in negative material is different.Fig. 5 is the cell testing results of preparation in embodiment 2 (NMC-porous silicon adds lithium powder-1), embodiment 3 (NMC-porous silicon adds lithium powder-2) and comparative example 2 (NMC-porous silicon), comprises specific discharge capacity and coulombic efficiency.As can be seen from the figure, add the first discharge specific capacity after the coated lithium material of lithium phosphate all at about 140mAh/g, 5 circulations remain on about 120mAh/g later substantially; The first discharge specific capacity of not adding the coated lithium material of lithium phosphate at about 45mAh/g, through 5 times circulation after lower than 30mAh/g.Add the coulombic efficiency first after the coated lithium material of lithium phosphate all more than 60%, and the coulombic efficiency first not adding the coated lithium material of lithium phosphate is only 21%.
In above-mentioned test, namely the battery prepared in comparative example 2 (NMC-porous silicon) is charged to 3.9V terminates.In embodiment and comparative example, we adopt identical electrode active material, and difference is only that the amount whether being added with the coated lithium material of lithium phosphate and interpolation in negative material is different.Therefore, can judge that the balance of itself and full anode and negative pole is relative, also demonstrate the effect of adding the coated lithium material of lithium phosphate porous silicon from another angle simultaneously.
Can prove from above-described embodiment, the lithium powder chemical property after coated can't be affected, and more stable, as lithium ion battery negative material additive, effectively can improve discharge capacity and the coulombic efficiency first of battery.
Claims (16)
1. a negative material additive, is characterized in that, described negative material additive is the lithium that Surface coating has lithium phosphate coating layer.
2. negative material additive according to claim 1, is characterized in that, the thickness of described lithium phosphate coating layer is 1nm ~ 10 μm.
3. negative material additive according to claim 2, is characterized in that, the thickness of described lithium phosphate coating layer is 50nm ~ 1 μm.
4. the preparation method of a negative material additive according to claim 1, comprise: a kind of organic solvent is provided, respectively lithium powder and pure phosphoric acid are added in described organic solvent and react, by removal of solvents after having reacted, obtain the lithium that Surface coating has lithium phosphate coating layer.
5. the preparation method of negative material additive according to claim 4, is characterized in that, the thickness of described lithium phosphate coating layer is 1nm ~ 10 μm.
6. the preparation method of negative material additive according to claim 5, is characterized in that, the thickness of described lithium phosphate coating layer is 50nm ~ 1 μm.
7. the preparation method of negative material additive according to claim 4, is characterized in that, at least one in the alkane that described organic solvent is selected from ether, carbon number is 7-20, aromatic hydrocarbons, sulfone class organic solvent.
8. the preparation method of negative material additive according to claim 7, is characterized in that, described organic solvent is ether.
9. the preparation method of negative material additive according to claim 8, is characterized in that, described organic solvent is oxolane.
10. the preparation method of negative material additive according to claim 7, is characterized in that, described organic solvent is sulfolane.
The preparation method of 11. negative material additives according to claim 4, is characterized in that, the particle diameter of described lithium powder is 10nm ~ 100 μm.
The preparation method of 12. negative material additives according to claim 11, is characterized in that, the particle diameter of described lithium powder is 0.5 ~ 10 μm.
The preparation method of 13. negative material additives according to claim 4, is characterized in that, described pure phosphoric acid is 1:100 ~ 1:5 with the mole ratio of lithium.
The preparation method of 14. negative material additives according to claim 13, is characterized in that, described pure phosphoric acid is 1:60 ~ 1:9 with the mole ratio of lithium.
The preparation method of 15. negative material additives according to claim 4, it is characterized in that, described pure phosphoric acid is adopted and is prepared with the following method: in deionized water or in phosphoric acid solution, add enough phosphorus pentoxides, 60 ~ 100 DEG C of heating, make water and phosphorus pentoxide complete reaction, obtain pure phosphoric acid.
16. 1 kinds of lithium ion batteries, the negative pole of described lithium ion battery includes negative material and negative material additive, and described negative material additive is the lithium that Surface coating has lithium phosphate coating layer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107546362A (en) * | 2017-07-17 | 2018-01-05 | 上海工程技术大学 | A kind of electrode with pyroelectric effect and its preparation method and application |
| CN108564197A (en) * | 2018-03-06 | 2018-09-21 | 大同新成新材料股份有限公司 | A kind of optimization method of battery negative electrode additive selection |
| JP2019079645A (en) * | 2017-10-23 | 2019-05-23 | 株式会社Ｇｓユアサ | Power storage element, method for manufacturing the same |
| CN112993233A (en) * | 2021-02-20 | 2021-06-18 | 昆山宝创新能源科技有限公司 | Lithium supplement material of lithium ion battery and preparation method and application thereof |
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| JPH06279010A (en) * | 1993-03-24 | 1994-10-04 | Central Glass Co Ltd | Stabilized lithium hexafluorophosphate |
| CN101522343A (en) * | 2006-10-13 | 2009-09-02 | Fmc公司-锂部 | Stabilized lithium metal powder for Li-ion application, composition and process |
| CN103447541A (en) * | 2007-05-16 | 2013-12-18 | Fmc公司 | Stabilized lithium metal powder for li-ion application, composition and method |
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| JPH06279010A (en) * | 1993-03-24 | 1994-10-04 | Central Glass Co Ltd | Stabilized lithium hexafluorophosphate |
| CN101522343A (en) * | 2006-10-13 | 2009-09-02 | Fmc公司-锂部 | Stabilized lithium metal powder for Li-ion application, composition and process |
| CN103447541A (en) * | 2007-05-16 | 2013-12-18 | Fmc公司 | Stabilized lithium metal powder for li-ion application, composition and method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107546362A (en) * | 2017-07-17 | 2018-01-05 | 上海工程技术大学 | A kind of electrode with pyroelectric effect and its preparation method and application |
| JP2019079645A (en) * | 2017-10-23 | 2019-05-23 | 株式会社Ｇｓユアサ | Power storage element, method for manufacturing the same |
| JP7096991B2 (en) | 2017-10-23 | 2022-07-07 | 株式会社Ｇｓユアサ | Power storage element and manufacturing method of power storage element |
| CN108564197A (en) * | 2018-03-06 | 2018-09-21 | 大同新成新材料股份有限公司 | A kind of optimization method of battery negative electrode additive selection |
| CN112993233A (en) * | 2021-02-20 | 2021-06-18 | 昆山宝创新能源科技有限公司 | Lithium supplement material of lithium ion battery and preparation method and application thereof |
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| CN105098189B (en) | 2018-02-16 |
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Effective date of registration: 20230506 Address after: 1080 Greenwood Avenue, Lake Mary, Florida, USA Patentee after: Weihong Advanced Materials Co. Address before: 313000 No. 2198 Hongfeng Road, Huzhou Economic and Technological Development Zone, Zhejiang Province Patentee before: MICROVAST POWER SYSTEMS Co.,Ltd. |
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