CN105098189B - Negative material additive and preparation method thereof - Google Patents
Negative material additive and preparation method thereof Download PDFInfo
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- CN105098189B CN105098189B CN201410216684.9A CN201410216684A CN105098189B CN 105098189 B CN105098189 B CN 105098189B CN 201410216684 A CN201410216684 A CN 201410216684A CN 105098189 B CN105098189 B CN 105098189B
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- lithium
- negative material
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- material additive
- phosphoric acid
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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 a kind of negative material additive and preparation method thereof, the negative material additive is the lithium that Surface coating has lithium phosphate clad.Lithium material is coated by lithium phosphate produced by the present invention, as negative material additive, efficiently solves the problem of lithium ion battery first charge-discharge efficiency is low.
Description
Technical field
The present invention relates to a kind of negative material additive and preparation method thereof.
Background technology
To have that voltage is high, energy density is big, service life is long, pollution-free and self discharge is small etc. excellent due to it for lithium ion battery
Point, is widely used in portable electric appts and electric automobile.At present, the negative material of commercial li-ion battery is mainly graphite
Negative material, its theoretical capacity are 372mAh/g, and actual development is already close to theoretical capacity, can development space it is limited,
Demand of the electric automobile to high-capacity high-power lithium ion battery is not adapted to.
Some new negative materials can have very high theoretical capacity, for example the theoretical capacity of silicon is 4200mAh/g,
But its first charge-discharge efficiency is all than relatively low.When these negative materials match into battery with positive electrode, substantial amounts of lithium ion
Just it is consumed after being charged in first time and positive pole can not be returned to.The original purpose for using Large Copacity negative pole is exactly to increase battery
Population size, but the low actual capacity that can seriously reduce lithium battery on the contrary of first charge-discharge efficiency, limit its application.
The loss of irreversible capacity first directly results in the loss of the energy content of battery in lithium battery.Capacitance loss is actually
It is the loss of lithium, for example efficiency is 75% first, then 25% lithium just irreversibly consumes after being charged in first time.Loss
Mostly come from the following aspects：1) fault of construction of positive pole, lithium ion can not smoothly depart from positive pole lattice structure or
Depart from after be not effectively reversible it is embedded；2) fault of construction of negative pole, the part lithium ion that negative pole is embedded into during charging are not effectively reversible
Ground deintercalation；3) part lithium ion forms SEI films in negative pole and positive electrode surface with electrolyte reaction.Generally, lithium is whole
Come from positive electrode, most expensive composition in this lithium battery.Lithium more than needed is added in cathode pole piece, is to solve this problem
Most direct generally the least expensive mode.But lithium metal is highly unstable in atmosphere, caused to actual production impassable
Obstacle.
At present, low have become of first charge-discharge efficiency hinders many negative materials, the especially negative material of Large Copacity
Realize the technical bottleneck of commercial applications.So there is an urgent need to develop a kind of effective and practical technology fundamentally to solve
The problem of certainly lithium battery first charge-discharge efficiency is low.
The content of the invention
The invention provides a kind of additive for lithium ion battery negative material, the additive application is in lithium-ion electric
Pond can effectively improve first charge-discharge efficiency.
According to the purpose of the present invention, negative material additive of the invention is the lithium that Surface coating has lithium phosphate clad.
According to one embodiment of the present invention, the thickness of above-mentioned lithium phosphate clad is 1nm~10 μm, preferably lithium phosphate
The thickness of clad is 50nm~1 μm.
It is a further object of the invention to provide a kind of preparation method of above-mentioned negative material additive, including：There is provided
A kind of organic solvent, lithium powder and pure phosphoric acid are added in the organic solvent reacted respectively, uniform stirring, after the completion of reaction
Solvent is removed, obtaining Surface coating has the lithium of lithium phosphate clad.
According to the embodiment of the present invention, alkane, aromatic hydrocarbons, the sulfone that above-mentioned organic solvent is selected from ether, carbon number is 7-20
At least one of class organic solvent etc..Preferably, above-mentioned organic solvent is ether；It is highly preferred that above-mentioned organic solvent is tetrahydrochysene
Furans.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 preferably the particle diameter of lithium powder is 0.5
~10 μm.
According to the embodiment of the present invention, wherein, the thickness of lithium phosphate clad is 1nm~10 μm, preferably lithium phosphate bag
The thickness of coating is 50nm~1 μm.The thickness of lithium phosphate clad can be controlled by the amount of the pure phosphoric acid of addition.In order to up to
To the purpose of the present invention, the mole ratio of above-mentioned pure phosphoric acid and lithium is 1:100~1:5, the preferably mole ratio of pure phosphoric acid and lithium
For 1:60~1:9.
According to the embodiment of the present invention, above-mentioned pure phosphoric acid can be prepared with the following method：To deionized water or phosphorus
Enough phosphorus pentoxides are added in acid solution (such as phosphoric acid solution that concentration is 85%), at 60~100 DEG C (such as 80 DEG C)
Heating, makes water and phosphorus pentoxide react completely, obtains pure phosphoric acid.
In the present invention, the addition sequence of pure phosphoric acid and lithium powder is not restricted by.The organic solution of pure phosphoric acid can be first configured,
Then lithium powder is added；First lithium powder can also be added in organic solvent, be slow added into pure phosphoric acid.In order to the phosphorus of acquisition
Sour lithium clad is more uniform, and accelerates reaction and carry out, and pure phosphoric acid or lithium powder are added preferably under stirring.
It is a further object of the invention to provide a kind of lithium ion battery, the negative pole of the lithium ion battery includes
Negative material and negative material additive, the negative material additive are the lithium powder that Surface coating has lithium phosphate clad.
According to one embodiment of the present invention, the negative material of the above-mentioned preferred Large Copacity of negative material, the negative pole material
Material can be selected from least one of graphite, silicon, tin, graphene, CNT, lithium titanate etc..
In order to solve problems of the prior art, the present invention is in the fine and close Li of lithium metal outer wrap3PO4Clad,
The clad can stop invasion and attack of the moisture in air to lithium metal so that lithium powder can be mixed into negative pole pole in normal conditions
Piece, and lithium battery is prepared in normal conditions.Lithium material is coated by the obtained lithium phosphate of the present invention, added as negative material
Agent, efficiently solve the problem of lithium ion battery first charge-discharge efficiency is low.
Brief description of the drawings
Fig. 1：The lithium phosphate cladding lithium material XRD spectra prepared in embodiment 1；
Fig. 2：Embodiment 1 and the button electrical test results (specific capacity) prepared in comparative example 1；
Fig. 3：Embodiment 1 and the button electrical test results (being pressed in electric discharge) prepared in comparative example 1；
Fig. 4：The lithium phosphate cladding lithium material SEM figures prepared in embodiment 1；
Fig. 5：The cell testing results prepared in embodiment 2, embodiment 3 and comparative example 2.
Embodiment
The present invention is described in detail following specific embodiment, but the present invention is not restricted to following implementation
Example.
It is prepared by pure phosphoric acid：Enough phosphorus pentoxides are added in 85% phosphoric acid solution, in 80 DEG C of heating, make water and five oxygen
Change two phosphorus to react completely, obtain pure phosphoric acid.
Operation sequence：Using tetrahydrofuran solution as solvent, appropriate lithium is impregnated；Pure phosphoric acid is gradually added into again, during reaction
Agitating solution.
Embodiment 1：
The tetrahydrofuran solution that pure phosphoric acid concentration is 10% (phosphoric acid 0.28g, tetrahydrofuran 2.5g) is prepared in glove box,
Stir, be slowly added to the lithium piece of 0.06g crushing, agitating solution, treat that tetrahydrofuran volatilizees completely, obtain lithium phosphate cladding lithium
Material.
The lithium phosphate cladding lithium material of above-mentioned preparation is subjected to XRD analysis, as a result as shown in Figure 1：There is Li in spectrogram3PO4It is special
Levy the presence at peak, it was demonstrated that there is Li on lithium surface3PO4Clad generates.
Detain electrically prepared：According to nickel-cobalt lithium manganate cathode material (NCM)/conductive agent/PVDF=8:1:1 ratio prepares slurry
Material, anode pole piece is made by being coated with, drying and cut into slices, cathode pole piece is to coat lithium material pressure using the lithium phosphate of above-mentioned preparation
Manufactured pole piece, electrolyte use il electrolyte, and above-mentioned anode pole piece, cathode pole piece and electrolyte are assembled into button
Battery carries out electrochemical property test.
Comparative example 1：
It is other to use material same as Example 1 in addition to cathode pole piece is the lithium piece suppressed using uncoated lithium powder
Material and technique prepare button cell.
Electrical test results are detained in embodiment 1 and comparative example 1 as shown in Figures 2 and 3.Wherein lithium powder piece is Li3PO4Coat lithium
Material compacting forms, and is showed with the lithium piece of uncoated mistake in NCM half-cells closely similar.Illustrate Li3PO4Do not influence lithium piece
Electrochemical effect.
Fig. 4 is that the lithium phosphate prepared in embodiment 1 coats lithium material SEM figures, it can be seen that on the surface of lithium powder
Structural integrity and continuous clad are formd, with reference to XRD test result, it is lithium phosphate that can prove the clad.
From the point of view of from the above, the lithium metal that coated can equally play the effect as uncoated lithium metal,
That is cladding adds the stability of 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 the lithium phosphate added with 10wt%
Lithium material (prepared by embodiment 1) is coated, battery is assembled into using lithium hexafluoro phosphate carbonic ester electrolyte and PVDF barrier films, it is put
Electric specific capacity and the test result of coulombic efficiency are as shown in Figure 5.
Embodiment 3：
With nickle cobalt lithium manganate (NCM) for positive electrode, porous silicon is negative material, wherein the lithium phosphate added with 20wt%
Lithium material (prepared by embodiment 1) is coated, battery is assembled into using lithium hexafluoro phosphate carbonic ester electrolyte and PVDF barrier films, it is put
Electric specific capacity and the test result of coulombic efficiency are as shown in Figure 5.
Comparative example 2：
With nickle cobalt lithium manganate (NCM) for positive electrode, porous silicon is negative material, is electrolysed using lithium hexafluoro phosphate carbonic ester
Liquid and PVDF barrier films are assembled into battery, as shown in Figure 5 to the test result of its specific discharge capacity and coulombic efficiency.
Test condition：
First time discharge and recharge：First carry out being charged to 4.3V with 0.1C multiplying powers, be then less than in 4.3V constant-voltage charges to electric current
0.01mA complete charges；Then discharged with 0.1C, blanking voltage 2.5V；
Second of discharge and recharge：First carry out being charged to 4.3V with 0.2C multiplying powers, be then less than in 4.3V constant-voltage charges to electric current
0.01mA complete charges；Then discharged with 0.2C, blanking voltage 2.5V；
Third time discharge and recharge：First carry out being charged to 4.3V with 0.2C multiplying powers, be then less than in 4.3V constant-voltage charges to electric current
0.01mA complete charges；Then discharged with 1.0C, blanking voltage 2.5V；
4th discharge and recharge：First carry out being charged to 4.3V with 0.2C multiplying powers, be then less than in 4.3V constant-voltage charges to electric current
0.01mA complete charges；Then discharged with 5.0C, blanking voltage 2.5V；
5th time and later discharge and recharge：First carry out being charged to 4.3V with 1.0C multiplying powers, then in 4.3V constant-voltage charges to electricity
Stream is less than 0.01mA complete charges；Then discharged with 1.0C, blanking voltage 2.5V.
Whether embodiment 2, embodiment 3 and differing only in for comparative example 2 are added with lithium phosphate cladding lithium in negative material
Material and the amount of addition are different.Fig. 5 is embodiment 2 (NMC- porous silicons add lithium powder -1), (NMC- porous silicons add lithium to embodiment 3
Powder -2) and the middle cell testing results prepared of comparative example 2 (NMC- porous silicons), including specific discharge capacity and coulombic efficiency.From figure
In as can be seen that the first discharge specific capacity after addition lithium phosphate cladding lithium material all in 140mAh/g or so, after 5 circulations
Substantially remain in 120mAh/g or so；The first discharge specific capacity of lithium phosphate cladding lithium material is not added with 45mAh/g or so, warp
It is less than 30mAh/g after crossing 5 circulations.The coulombic efficiency first after lithium phosphate cladding lithium material is added all more than 60%, and not
The coulombic efficiency first for adding lithium phosphate cladding lithium material is only 21%.
In above-mentioned test, the battery of preparation is charged to 3.9V and terminated in comparative example 2 (NMC- porous silicons).Embodiment and right
Whether we use identical electrode active material in ratio, differ only in negative material added with lithium phosphate cladding lithium material
Material and the amount of addition are different.Therefore, it is possible to judge that the balance of itself and full anode and negative pole is relative, while
The effect that lithium phosphate cladding lithium material is added in porous silicon is demonstrated from another angle.
It can be proved from above-described embodiment, the lithium powder chemical property after cladding can't be affected, and more steady
It is fixed, as lithium ion battery negative material additive, the discharge capacity and coulombic efficiency first of battery can be effectively improved.
Claims (9)
1. a kind of preparation method of negative material additive, including：A kind of organic solvent is provided, respectively added lithium powder and pure phosphoric acid
Enter and reacted in the organic solvent, remove solvent after the completion of reaction, obtaining Surface coating has the lithium of lithium phosphate clad；
The thickness of the lithium phosphate clad is 1nm~10 μm；The particle diameter of the lithium powder is 10nm~100 μm；The pure phosphoric acid and lithium
Mole ratio be 1:100~1:5.
2. the preparation method of negative material additive according to claim 1, it is characterised in that the lithium phosphate clad
Thickness be 50nm~1 μm.
3. the preparation method of negative material additive according to claim 1, it is characterised in that the organic solvent is selected from
Ether, carbon number are at least one of 7-20 alkane, aromatic hydrocarbons, sulfone class organic solvent.
4. the preparation method of negative material additive according to claim 3, it is characterised in that the organic solvent is
Ether.
5. the preparation method of negative material additive according to claim 4, it is characterised in that the organic solvent is four
Hydrogen furans.
6. the preparation method of negative material additive according to claim 3, it is characterised in that the organic solvent is ring
Fourth sulfone.
7. the preparation method of negative material additive according to claim 1, it is characterised in that the particle diameter of the lithium powder is
0.5~10 μm.
8. the preparation method of negative material additive according to claim 1, it is characterised in that the pure phosphoric acid and lithium
Mole ratio is 1:60~1:9.
9. the preparation method of negative material additive according to claim 1, it is characterised in that the pure phosphoric acid is using such as
It is prepared by lower method：Enough phosphorus pentoxides are added into deionized water or in phosphoric acid solution, in 60~100 DEG C of heating, are made
Water and phosphorus pentoxide react completely, obtain pure phosphoric acid.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| CN118658994A (en) * | 2024-08-05 | 2024-09-17 | 比亚迪股份有限公司 | Negative electrode sheet and preparation method thereof, battery and electrical equipment |
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|---|---|---|---|---|
| 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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| JP2898163B2 (en) * | 1993-03-24 | 1999-05-31 | セントラル硝子株式会社 | Stabilized lithium hexafluorophosphate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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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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