CN107565119A - A kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery - Google Patents
A kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery Download PDFInfo
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- CN107565119A CN107565119A CN201610498757.7A CN201610498757A CN107565119A CN 107565119 A CN107565119 A CN 107565119A CN 201610498757 A CN201610498757 A CN 201610498757A CN 107565119 A CN107565119 A CN 107565119A
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- lithium molybdate
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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 present invention relates to a kind of bar-shaped lithium molybdate negative active core-shell material, the bar-shaped lithium molybdate is micron order club shaped structure；A diameter of 12 μm of the bar-shaped lithium molybdate；Length is 17 μm.The present invention also provides a kind of preparation method of bar-shaped lithium molybdate negative active core-shell material and a kind of lithium ion battery.For the present invention by using the bar-shaped lithium molybdate of micron order as negative active core-shell material, particle diameter is smaller, is advantageous to the deintercalation of lithium ion, simultaneously solid structure advantageously reduces the specific surface area of material, side reaction is reduced, improves the compacted density and volume and capacity ratio of material, and preparation technology is simple.
Description
Technical field
The present invention relates to a kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery.
Background technology
Lithium ion battery experienced the time less than 20 years from birth till now, and its application field is from initial shifting
It is dynamic communication be rapidly spread to including various portable type electronic products be related to people's life ＆ amusement, military affairs, Aero-Space,
Medical treatment, the various aspects of communication, and develop to big-and-middle-sized energy storage device and electrical source of power etc..Lithium ion battery is in business
In industry acquired immense success and the promotion to the development of above-mentioned field be any secondary cell it is incomparable.
Prior art（201310237337.X）In disclose a kind of lithium ion battery molybdic acid lithium titanate cathode material preparation
Method, lithium salts, molybdenum salt precursor are stoichiometrically counted into ratio（Mol ratio）Uniformly mix, being heated to 200-400 DEG C in air enters
Row insulation pretreatment, then in atmosphere or in nitrogen, argon gas, carbon dioxide inert atmosphere, is carried out under the conditions of 500-800 DEG C
Sintering reaction, obtain the lithium molybdate of lithium ion battery（Li2MoO4）Negative material.But molybdic acid cathode of lithium prepared by high temperature solid-state method
There are many shortcomings in material, raw material is difficult to reach the uniform mixing on atomic level, and high temperature sintering causes particle size larger, no
Beneficial to the deintercalation of lithium ion, molybdic acid lithium titanate cathode material performance is had a great influence.
Prior art（201310237338.4）In disclose the sol-gel of another lithium ion battery molybdic acid cathode of lithium
Preparation method, by MoO3Powder, which is dissolved in distilled water, to be placed in uniform stirring on magnetic stirring apparatus and is heated to 80 DEG C of formation canescence
Suspension solution, lithium salts is added, the colloid of stable homogeneous is eventually formed, after vacuum drying, obtains lithium molybdate（Li2MoO4）Negative pole material
Material.Resulting materials are to be about 5 μm of tubular morphology, and particle diameter is smaller, are advantageous to be lifted the chemical property of material.But tubular shape
Looks cause that its specific surface area is larger, and compacted density is relatively low, and so as to cause side reaction more, volume and capacity ratio is relatively low.
The content of the invention
Lithium molybdate electrode material has that particle diameter is larger, and specific surface area is larger to the present invention to solve in the prior art, is unfavorable for
The deintercalation of lithium ion, compacted density is relatively low, and so as to cause side reaction more, volume and capacity ratio is relatively low.A kind of particle diameter is especially provided
It is smaller, be advantageous to the deintercalation of lithium ion, while the specific surface area of material is advantageously reduced, side reaction is reduced, improves the pressure of material
Real density and volume and capacity ratio, the negative active core-shell material of the simple micron order club shaped structure of preparation technology and preparation method thereof and one
Kind lithium ion battery.
To solve the above problems, the present invention provides a kind of bar-shaped lithium molybdate negative active core-shell material, the bar-shaped lithium molybdate is
Micron order club shaped structure；A diameter of 1-2 μm of the bar-shaped lithium molybdate；Length is 1-7 μm.
The present invention also provides a kind of preparation method of bar-shaped lithium molybdate negative active core-shell material, and step includes：
S1, big particle diameter lithium molybdate mixed with the mixed solution of water and polyalcohol；
S2, heating, cooling, separate to obtain bar-shaped lithium molybdate negative active core-shell material.
A kind of lithium ion battery, including housing and be contained in housing battery core, electrolyte, battery core include positive pole, negative pole
And the barrier film between positive pole and negative pole；The negative pole includes negative current collector and negative material；The negative material includes
Negative active core-shell material, wherein, the negative active core-shell material is negative active core-shell material as described above.
For the present invention using bar-shaped lithium molybdate as negative active core-shell material, the particle diameter of bar-shaped lithium molybdate is small, is advantageous to lithium ion
Deintercalation, while advantageously reduce the specific surface area of material, reduce side reaction, improve the compacted density and volume specific volume of material
Amount.Big particle diameter lithium molybdate is dissolved in water and polynary mixed alkoxide solution, big particle diameter lithium molybdate is dissolved in water and does not dissolve in polyalcohol, polynary
Alcohol can suppress Li2MoO4The growth of crystal grain, while play a part of structure directing and dispersant.On the one hand, the hydroxyl in polyalcohol
Base adsorbing metal ions, make its that linear array be presented, beneficial to forming sheet and Rod-like shape.On the other hand, polyalcohol can make
Raw material is dispersed in the mixed solution of polyalcohol and water, and with the rise of temperature, the content of mixed solution reclaimed water is increasingly
Low, when reaching hypersaturated state, Li will be made by continuing heating2MoO4There is precipitation in each position, in the absence of bulky grain.Most
Afterwards, water content is very low in the clear liquid after separation, predominantly polyalcohol, can reclaim and be continuing with, and will not cause to waste.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the bar-shaped lithium molybdate negative active core-shell material S1 of gained in the embodiment of the present invention 1；
Fig. 2 is battery S10 of the present invention charging and discharging curve；
Fig. 3 is battery S10 and DS20 of the present invention cycle life curve.
Embodiment
The present invention provides a kind of bar-shaped lithium molybdate negative active core-shell material, and the bar-shaped lithium molybdate is micron order club shaped structure；It is described
A diameter of 1-2 μm of bar-shaped lithium molybdate；Length is 1-7 μm.The particle diameter of bar-shaped lithium molybdate is small, is advantageous to the deintercalation of lithium ion, together
Shi Shixin structure advantageously reduces the specific surface area of material, reduces side reaction, improves the compacted density and volume specific volume of material
Amount.Diameter is big less than 100nm material specific surface area, and more side reaction can occur during as electrode material；Particle diameter is more than 10 μ
M material, it is unfavorable for the deintercalation of lithium ion, is also not suitable for as electrode material.
Invention also provides the preparation method of above-mentioned bar-shaped lithium molybdate negative active core-shell material, step includes：
S1, big particle diameter lithium molybdate mixed with the mixed solution of water and polyalcohol；
S2, heating, cooling, separate to obtain bar-shaped lithium molybdate negative active core-shell material.
Big particle diameter lithium molybdate is dissolved in water and polynary mixed alkoxide solution, big particle diameter lithium molybdate is dissolved in water insoluble in polynary
Alcohol, polyalcohol can suppress Li2MoO4The growth of crystal grain, while play a part of structure directing and dispersant.On the one hand, it is polynary
Hydroxyl adsorbing metal ions in alcohol, make its that linear array be presented, beneficial to forming sheet and Rod-like shape.On the other hand, it is polynary
Alcohol can be such that raw material is dispersed in the mixed solution of polyalcohol and water, and with the rise of temperature, mixed solution reclaimed water contains
Amount is more and more lower, and when reaching hypersaturated state, Li will be made by continuing heating2MoO4There is precipitation in each position, in the absence of big
Particle.Water content is very low in clear liquid after separation, predominantly polyalcohol, can reclaim and be continuing with, and will not cause to waste.Solve
Technical problem existing for molybdic acid lithium titanate cathode material prepared by high temperature solid-state method：Raw material is difficult to reach uniformly mixed on atomic level
Close, high temperature sintering causes particle size larger, is unfavorable for the deintercalation of lithium ion, the influence to molybdic acid lithium titanate cathode material performance compared with
Greatly.
It is preferred that big particle diameter lithium molybdate is the non-bar-shaped lithium molybdate of more than 10 μm of particle diameter, can commercially available from or voluntarily synthesize.
It is preferred that relative to the polyalcohol of 100 parts by weight, the amount of the big particle diameter lithium molybdate is 0.5-3 parts by weight.Further
It is preferred that the amount of the big particle diameter lithium molybdate of addition is 1-2 parts by weight.When the big particle diameter lithium molybdate entered is excessive, the solvent of same volume
In simultaneously separate out lithium molybdate it is more, be easy to grow into the product being relatively large in diameter.
It is preferred that water and the mass ratio of polynary mixed alkoxide solution reclaimed water and polyalcohol are 1:20-50.Mixed solvent reclaimed water is big
The carrier of particle diameter lithium molybdate, the solubility of big particle diameter lithium molybdate is larger, and less water can meets to require, and for phase homogeneity
The big particle diameter lithium molybdate of amount, the volume of dispersant polyalcohol is bigger, and the particle diameter of resulting bar-shaped lithium molybdate is smaller.
It is preferred that heating-up temperature is 180 ~ 250 DEG C, the heat time is 1 ~ 2h.Further preferably, the temperature of heating be 190 ~
200 DEG C, the time of heating is 1 ~ 2h.
It is preferred that hybrid mode can select the technologies commonly used in the art such as magnetic agitation.Separate mode uses this area
Conventional to use technology, the application is from centrifugation.
It is preferred that polyalcohol is selected from ethylene glycol（EG）, diglycol（DEG）, triethylene-glycol（TEG）With three contractings four
Ethylene glycol（TTEG）In one or more.
Present invention also offers a kind of lithium ion battery, including housing and be contained in housing battery core, electrolyte, battery core
Including positive pole, negative pole and the barrier film between positive pole and negative pole；Wherein negative pole includes negative current collector and negative material；Negative pole
Material includes negative active core-shell material, negative electrode binder, wherein, the negative active core-shell material is negative electrode active material of the present invention
Material；The being also an option that property of negative material includes conductive agent, and the conductive agent is conventional conductive agent, can be with positive electrode material layer
In conductive agent it is identical or different, the negative electrode binder can be negative electrode binder commonly used in the art.Positive pole includes
Plus plate current-collecting body and positive electrode, positive electrode include positive electrode active materials, conductive agent, positive electrode binder, the conductive agent, just
Pole binding agent can be conductive agent commonly used in the art, positive electrode binder；The electrolyte is commonly used in the art
Electrolyte；The barrier film is barrier film commonly used in the art.
Due to the preparation technology of negative plate, electrolyte, positive plate, barrier film technology well known in the art, and battery
Technology also well known in the art is assembled, is just repeated no more herein.
Below in conjunction with lithium ion of the specific embodiment to the negative active core-shell material of the present invention and containing the negative active core-shell material
Battery is described further.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit
The fixed present invention.Raw material is commercially available employed in embodiment and comparative example.
Embodiment 1
The big particle diameter lithium molybdate of high temperature solid-phase sintering product for weighing the big particle diameter lithium molybdates of 2g is dissolved in 6g water and 200g DEG mixing
In solution, magnetic agitation is cooled to room temperature after being heated to 200 DEG C of holding 1h, centrifuges, and ethanol cleaning, it is bar-shaped to obtain micron order
Lithium molybdate product, labeled as S1.The stereoscan photograph of S1 products is shown in Fig. 1.
A diameter of 1.5 ± 0.3 μm of obtained S1；Length is 5 μm.
Embodiment 2
The big particle diameter lithium molybdate of high temperature solid-phase sintering product for weighing the big particle diameter lithium molybdates of 4g is dissolved in 8g water and 200g TEG mixing
In solution, magnetic agitation is cooled to room temperature after being heated to 190 DEG C of holding 2h, centrifuges, and ethanol cleaning, it is bar-shaped to obtain micron order
Lithium molybdate product, labeled as S2.
A diameter of 1.7 ± 0.3 μm of obtained S2；Length is 7 μm.
Embodiment 3
The big particle diameter lithium molybdate of high temperature solid-phase sintering product for weighing the big particle diameter lithium molybdates of 6g is dissolved in 10g water and 200gEG mixing is molten
In liquid, magnetic agitation is cooled to room temperature after being heated to 180 DEG C of holding 2h, centrifuges, and ethanol cleaning, obtains the bar-shaped molybdenum of micron order
Sour lithium product, labeled as S3.
A diameter of 1.8 ± 0.3 μm of obtained S3；Length is 8 μm.
Embodiment 4
The high temperature solid-phase sintering product Li2MoO4 for weighing the big particle diameter lithium molybdates of 1g is dissolved in 4g water and 200gTTEG mixed solution
In, magnetic agitation is cooled to room temperature after being heated to 200 DEG C of holding 2h, centrifuges, and ethanol cleaning, obtains micron order club shaped structure
Li2MoO4 products, labeled as S4.
A diameter of 1.3 ± 0.3 μm of obtained S4；Length is 3 μm.
Embodiment 5
The high temperature solid-phase sintering product Li2MoO4 for weighing the big particle diameter lithium molybdates of 1g is dissolved in 3g water and 200gTTEG mixed solution
In, magnetic agitation is cooled to room temperature after being heated to 200 DEG C of holding 2h, centrifuges, and ethanol cleaning, obtains micron order club shaped structure
Li2MoO4 products, labeled as S5.
A diameter of 1.0 ± 0.3 μm of obtained S5；Length is 1 μm.
Comparative example 1
With reference to the patent of Application No. 201310237338.4, sol-gel process prepares Li2MoO4Material, labeled as DS1.
Obtained DS1 tubular morphologies, length are 5 μm.
Comparative example 2
With reference to Application No. 201310237337.X patent, high temperature solid-state method preparation method obtains Li2MoO4Material, it is labeled as
DS2
Obtained DS2 does not have regular shape, 10 ~ 30 μm of particle diameter.
Performance test
1st, sem test
Tester：JSM-7600F type field emission scanning electron microscopes
Method of testing：Above example 1 is taken to carry out Flied emission electron-microscope scanning test, 5000 times of amplification is micro- to negative active core-shell material S1
See pattern to be analyzed, therefore obtain Fig. 1；According to the method for testing of testing example 1, embodiment 2-5 and comparative example are measured
1-2。
Test result：Made negative active core-shell material S1 SEM photograph in embodiment 1, it is a diameter of 1.5 to show product
μm or so rod-shpaed particle, good dispersion.
2nd, the making of battery：
Test cell positive plate difference electrode active material in mass ratio（S1-S5 is taken successively）:Acetylene black:PVDF= 85:10:5
Ratio it is well mixed after tabletting be made, pole piece is dried in vacuo more than 24h in 120 DEG C.Using metal lithium sheet as negative pole,
Celgard2400 polypropylene porous films are barrier film, 1mol/L LiPF6 ethylene carbonate (EC) and dimethyl carbonate
(DMC) (volume ratio is=1 to mixed solution:1) it is electrolyte.The assembling process of all batteries is in the glove box full of argon gas
Middle progress, obtains battery sample S10-S50 successively.
Battery sample DS10- DS20 are prepared using above-mentioned identical method, difference is：Electrode active material is
DS1- DS2。
3rd, electrochemical property test
Test equipment：Rechargeable battery performance detection apparatus BK-6808AR/2mA (blue odd electron Industrial Co., Ltd.).
Method of testing：5min is shelved, with the embedding lithiums of 0.1C, blanking voltage 0.1V.After shelving 10min, lithium is taken off with 0.1C, taken off
Lithium blanking voltage 2.5V.Charge-discharge magnification is set as 0.5C during circulation, and circulation work step is set as 50 circulations.
Battery sample S10-S50 and DS10- DS20 charge/discharge capacity are tested using the method for testing and circulated 50 times
Charge/discharge capacity and capability retention, test result is shown in Table 1.
Wherein, specific discharge capacity includes the embedding lithium capacity of mass ratio（Discharge capacity）, mass ratio take off lithium capacity（Charging capacity）,
The computational methods that the embedding lithium capacity of the mass ratio, mass ratio take off lithium capacity are obtained according to embedding lithium capacity and de- lithium calculation of capacity, are
Survey the ratio of removal lithium embedded capacity and the actual activity substance content adhered to of pole piece.Capability retention is to discharge to hold after circulating 50 times
The percentage of amount and first discharge capacity.
Fig. 2 is the charging and discharging curve in charge-discharge magnification 0.1C using the battery sample S10 made by S1.It can send out
Existing, S10 discharge capacity first is 1133.7mAh/g, and initial charge capacity is 823.6mAh/g, and second of discharge capacity is
806.0mAh/g.The test result of each battery such as table 1 below.
。
The battery sample being prepared it can be seen from the test result of table 1 using preparation method provided by the invention
S10-S50, its charge/discharge capacity are high, hence it is evident that better than the battery sample DS10- DS20 of comparative example.
Fig. 3 is using battery S10 made by S1 and the cycle life curve using made battery DS20 in DS2, S10 electricity
Discharge capacity is 543.3mAh/g after pond is circulated 50 times, capability retention 47.9%, discharge capacity after DS20 circulating batteries 50 times
For 149.2mAh/g, capability retention 18.5%, show that the negative active core-shell material for the micron order club shaped structure that this patent provides has
There are higher discharge capacity and good charge and discharge cycles stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in protection scope of the present invention.
Claims (9)
1. a kind of bar-shaped lithium molybdate negative active core-shell material, it is characterised in that the bar-shaped lithium molybdate is micron order club shaped structure；Institute
State bar-shaped lithium molybdate a diameter of 1-2 μm；Length is 1-7 μm.
A kind of 2. preparation method of bar-shaped lithium molybdate negative active core-shell material as claimed in claim 1, it is characterised in that step bag
Include：
S1, big particle diameter lithium molybdate mixed with the mixed solution of water and polyalcohol；
S2, heating, cooling, separate to obtain bar-shaped lithium molybdate negative active core-shell material.
3. the preparation method of bar-shaped lithium molybdate negative active core-shell material according to claim 2, it is characterised in that described big
Particle diameter lithium molybdate is the non-bar-shaped lithium molybdate of more than 10 μm of particle diameter.
4. the preparation method of bar-shaped lithium molybdate negative active core-shell material according to claim 2, it is characterised in that relative to
The polyalcohol of 100 parts by weight, the amount of the big particle diameter lithium molybdate is 0.5-3 parts by weight.
5. the preparation method of bar-shaped lithium molybdate negative active core-shell material according to claim 4, it is characterised in that relative to
The polyalcohol of 100 parts by weight, the amount of the big particle diameter lithium molybdate is 1-2 parts by weight.
6. the preparation method of bar-shaped lithium molybdate negative active core-shell material according to claim 2, it is characterised in that the water
It is 1 with the mixed solution reclaimed water of polyalcohol and the mass ratio of polyalcohol:20-50.
7. the preparation method of bar-shaped lithium molybdate negative active core-shell material according to claim 2, it is characterised in that the heating
Temperature be 180 ~ 250 DEG C, the time of heating is 1 ~ 2h.
8. the preparation method of bar-shaped lithium molybdate negative active core-shell material according to claim 2, it is characterised in that described more
First alcohol is selected from ethylene glycol, diglycol, the one or more in triethylene-glycol and tetraethylene-glycol.
9. a kind of lithium ion battery, including housing and be contained in housing battery core, electrolyte, battery core include positive pole, negative pole and
Barrier film between positive pole and negative pole；The negative pole includes negative current collector and negative material；The negative material includes negative
Pole active material, it is characterised in that negative active core-shell material of the negative active core-shell material as described in claim any one of 1-8.
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| CN201610498757.7A CN107565119B (en) | 2016-06-30 | 2016-06-30 | Negative electrode active material, preparation method thereof and lithium ion battery |
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| CN201610498757.7A CN107565119B (en) | 2016-06-30 | 2016-06-30 | Negative electrode active material, preparation method thereof and lithium ion battery |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241642A (en) * | 2013-06-17 | 2014-12-24 | 华南理工大学 | Lithium molybdate cathode material for lithium ion battery and preparation method thereof |
| CN104229894A (en) * | 2013-06-17 | 2014-12-24 | 华南理工大学 | Sol-gel method for preparation of lithium ion battery lithium molybdate cathode material |
| CN104577088A (en) * | 2013-10-16 | 2015-04-29 | 中国科学院物理研究所 | Lithium molybdate serving as secondary battery electrode material |
-
2016
- 2016-06-30 CN CN201610498757.7A patent/CN107565119B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241642A (en) * | 2013-06-17 | 2014-12-24 | 华南理工大学 | Lithium molybdate cathode material for lithium ion battery and preparation method thereof |
| CN104229894A (en) * | 2013-06-17 | 2014-12-24 | 华南理工大学 | Sol-gel method for preparation of lithium ion battery lithium molybdate cathode material |
| CN104577088A (en) * | 2013-10-16 | 2015-04-29 | 中国科学院物理研究所 | Lithium molybdate serving as secondary battery electrode material |
Non-Patent Citations (2)
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| MOHAMMAD RAMZAN PARRA等: "Poly(Ethylene Glycol)(PEG)-assisted shape-controlled synthesis", 《OPTIK》 * |
| XUDONG LIU等: "Synthesis of One Dimensional Li2MoO4 Nanostructures and Their Electrochemical Performance as Anode Materials for Lithium-ion Batteries", 《ELECTROCHIMICA ACTA》 * |
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