CN109935789A - A kind of lithium ion battery negative material and preparation and application - Google Patents
A kind of lithium ion battery negative material and preparation and application Download PDFInfo
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- CN109935789A CN109935789A CN201711344346.3A CN201711344346A CN109935789A CN 109935789 A CN109935789 A CN 109935789A CN 201711344346 A CN201711344346 A CN 201711344346A CN 109935789 A CN109935789 A CN 109935789A
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Abstract
A kind of lithium ion battery negative material, using porous graphene as conducting matrix grain, the silicon nano of Nafion cladding is attached on conducting matrix grain.The present invention coats silicon nano with Nafion, forms flexible clad, can accommodate volume expansion of the silicon in charge and discharge process, and the structure of Nafion can promote lithium ion in the transmission of electrolyte and electrode interface；Simultaneously using porous graphene as conducting matrix grain, enhance the electric conductivity of electrode material.Compared with prior art: Nafion clad has certain flexibility, can accommodate volume expansion of the silicon in charge and discharge process, improve the cycle performance of battery；The molecular structure of Nafion can promote lithium ion in the transmission of electrolyte and electrode interface, improve the high rate performance of battery；Graphene conductive skeleton can enhance the electric conductivity of electrode material.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to the negative electrode material and its preparation of lithium ion battery
Method.
Background technique
Lithium ion battery is a kind of rechargeable battery, and lithium ion movement between positive and negative anodes is relied in charge and discharge process
At work.Application of the lithium ion battery in the energy storage fields such as portable electronic device, power vehicle becomes increasingly popular, and develops higher
The lithium ion battery of energy density and power density is also at the important research direction in current energy storage scientific and technical research.And lithium ion
The further development of battery is heavily dependent on the capacity of negative electrode material and substantially proposing for high magnification heavy-current discharge performance
It rises.Currently, commercialization graphite negative electrodes material limits the promotion of battery capacity due to the bottleneck of theoretical capacity (372mA h/g).
On the other hand, graphite cathode will form Li dendrite in charge and discharge process, and then pierces through diaphragm and lead to battery short circuit or even quick-fried
It is fried, safe threat is caused to using.Therefore, develop large capacity, the negative electrode material of high safety becomes Study on Li-ion batteries
Emphasis.The higher alloy material of cathode of the specific discharge capacities such as aluminium, silicon, tin is by biggish concern, wherein silicon is held due to its theory
Amount is up to 4200mA h/g (Li22Si5), and lower (the 0.2V vs.Li of intercalation potential+/ Li), it is considered as most potential high energy
Measure negative electrode material.
Although silicon based anode material theoretical discharge capacity is higher and intercalation potential is lower, itself there are conductivity compared with
Low (10-3) and diffusion coefficient low (10 of the lithium ion in body phase silicon S/cm-14~10-13cm2/ s) the shortcomings that.And it is caused to follow
Ring performance declines main the reason is that silicon volume expansion during embedding lithium is up to 300%, and de- lithium is shunk in the process, in turn
Material dusting, material and collector, which are lost, to be in electrical contact, and the LiPF in the silicon face and electrolyte being exposed6It decomposes and generates
HF react, prevent silicon face from forming stable solid electrolyte film, constantly consumption electrolyte, cause circulating battery steady
Qualitative and cycle performance is deteriorated.In view of the above-mentioned problems, researchers propose various micro-/micro-nano structures and table/interfacial structure to silicon
It is modified, comprising: 1. nanoparticle, core-shell structure etc.；2. porous silicon；3. nano wire, nanotube, nanofiber etc.；4. silicon
Base complex, including silicon/carbon, silicon/polymer, silicon/metal, silicon/intermetallic compound.In recent years, the research of silicon-based anode
The nanostructure for achieving significant progress and great breakthrough: being inspired by garnet and designed, with C/2 rate charge-discharge circulation
1000 times, specific capacity and volume capacity respectively reach 1160mA h/g and 1270mA h/cm3；Micropore Si/C material is in 400mA/g
Charge and discharge cycles 150 times under current density, specific capacity and volume capacity are respectively 1600mA h/g and 1088mA h/cm3；It is low at
Originally, bivalve Si@SiOx@C core-shell structure recycles 100 specific capacities under 100mA/g and 500mA/g current density and respectively reaches
1450mA h/g and 1230mA h/g.
Summary of the invention
This patent coats silicon nano with Nafion, forms flexible clad, can accommodate silicon in charge and discharge process
Volume expansion, and the structure of Nafion can promote lithium ion in the transmission of electrolyte and electrode interface；Simultaneously using more
Hole graphene enhances the electric conductivity of electrode material as conducting matrix grain.
A kind of lithium ion battery negative material, using porous graphene as conducting matrix grain, the silicon nanoparticle of Nafion cladding
Son is attached on conducting matrix grain.
Silicon nano partial size is 30-100nm, and the mass ratio of Nafion clad and silicon nano is 1:5-3:5.
The silicon nano of Nafion cladding and the mass ratio of conducting matrix grain are 7:1-9:1.
The cathode material preparation method, includes the following steps,
1) Nafion coats the preparation of silicon nano: it disperses silicon nano in the aqueous isopropanol of Nafion,
It is ground after drying up to product；
2) preparation of porous graphene: graphite oxide first is synthesized with Hummer method, the graphite oxide is added in water and obtains
Graphite oxide dispersion, the concentration of graphite oxide dispersion are 0.5-1.5mg/mL, and ultrasound removing, then freeze-drying obtains more
Hole graphite oxide；The H at 900-1100 DEG C2It is restored in atmosphere, obtains porous graphene；
3) Nafion made from step 1) preparation of the Nafion cladding nano-silicon of porous graphene support: is coated into nanometer
The porous graphene high speed ball milling of silicon and step 2) preparation, obtains final product.
Step 1) the silicon nano partial size is 30-100nm；Nafion mass in the aqueous isopropanol of the Nafion
Mass ratio with silicon nano is 1:5-3:5.
The mass concentration 3%-10% of the aqueous isopropanol of the step 1) Nafion.
The time of step 2) the ultrasound removing is 1-3h；The H2Recovery time in atmosphere is 1-2h.
The freeze-drying condition is -50 DEG C -- 55 DEG C, 600-200Pa, the time of freeze-drying are 1-4 days.
The mass ratio of step 3) the Nafion cladding nano-silicon and porous graphene is 7:1-9:1；The high speed ball milling
Speed be 400-600rpm, time 8-12h；
Application of the negative electrode material in negative electrode of lithium ion battery.
Compared with prior art, the present invention has following technical advantage:
1.Nafion clad has certain flexibility, can accommodate volume expansion of the silicon in charge and discharge process, mention
The cycle performance of high battery；
The molecular structure of 2.Nafion can promote lithium ion in the transmission of electrolyte and electrode interface, improve times of battery
Rate performance；
3. the electric conductivity that graphene conductive skeleton can enhance electrode material.
Detailed description of the invention
Specific discharge capacity circulation figure when the material that Fig. 1 embodiment 1-3 is prepared is as lithium ion battery electrode material.
Wherein, this material and lithium piece are assembled into half-cell, and the carrying capacity of electrode material is 0.7mg/mm2, battery structure is
2032 button cells are tested under the charge-discharge magnification of 0.5C, and charge and discharge cycles 1000 are enclosed battery discharge specific capacity and are maintained at
500mAh/g, coulombic efficiency reach 99%.
Specific embodiment
Embodiment
1) silicon nano that quality is 0.1g is dispersed in the aqueous isopropanol of the Nafion of 0.04g mass concentration 5%
In, Nafion cladding silicon nano is ground to obtain after drying at room temperature；Wherein the diameter of silicon nano is 30-100nm；
2) graphite oxide is synthesized using Hummer method, it is (specific herein for being diluted to concentration with deionized water (solvent)
Value) 1mg/mL, ultrasound removing 1h, then freeze-drying (occurrence) 2 days under -52 DEG C, 300Pa, obtain porous oxidation graphite.
By obtained porous oxidation graphite in 1000 DEG C of H21h is restored in atmosphere, obtains porous graphene.
3) by the cladding nano-silicon of Nafion made from step 1) and the porous graphene of step 2 preparation according to mass ratio 85:
15 ball millings, obtain final product.
Comparative example
Method reported in article generally uses template and magnesium reduction process that silicon is made, and then mixes with graphite oxide,
Finally reduction obtains the mixture of silicon and graphene；Or one layer of carbon is wrapped up in silicon face in situ synthesis.In contrast, this is special
The method of benefit is simpler feasible, material short preparation period, is suitble to large scale preparation.
Claims (10)
1. a kind of lithium ion battery negative material, it is characterised in that:
Using porous graphene as conducting matrix grain, the silicon nano of Nafion cladding is attached on conducting matrix grain.
2. according to negative electrode material described in claim 1, it is characterised in that:
Silicon nano partial size is 30-100nm, and the mass ratio of Nafion clad and silicon nano is 1:5-3:5.
3. according to negative electrode material as claimed in claim 1 or 2, it is characterised in that: the silicon nano of Nafion cladding and conductive bone
The mass ratio of frame is 7:1-9:1.
4. a kind of any cathode material preparation method of claim 1-3, it is characterised in that: include the following steps,
1) Nafion coats the preparation of silicon nano:
It disperses silicon nano in the aqueous isopropanol of Nafion, is ground after dry up to product；
2) preparation of porous graphene:
Graphite oxide first is synthesized with Hummer method, the graphite oxide is added in water and obtains graphite oxide dispersion, graphite oxide
The concentration of dispersion liquid is 0.5-1.5mg/mL, and ultrasound removing, then freeze-drying obtains porous oxidation graphite；At 900-1100 DEG C
Lower H2It is restored in atmosphere, obtains porous graphene；
3) preparation of the Nafion cladding nano-silicon of porous graphene support:
By the porous graphene high speed ball milling of the cladding nano-silicon of Nafion made from step 1) and step 2) preparation, finally produced
Object.
5. cathode material preparation method as claimed in claim 4, it is characterised in that: step 1) the silicon nano partial size is
30-100nm；The mass ratio of Nafion mass and silicon nano is 1:5-3:5 in the aqueous isopropanol of the Nafion.
6. cathode material preparation method as claimed in claim 4, it is characterised in that: the aqueous isopropanol of the step 1) Nafion
Mass concentration 3%-10%.
7. cathode material preparation method as claimed in claim 4, it is characterised in that: the time of step 2) the ultrasound removing is 1-
3h；The H2Recovery time in atmosphere is 1-2h.
8. cathode material preparation method as claimed in claim 4, it is characterised in that: the freeze-drying condition is -50 DEG C -- 55
DEG C, 600-200Pa, time of freeze-drying is 1-4 days.
9. cathode material preparation method as claimed in claim 4, it is characterised in that: step 3) Nafion cladding nano-silicon with
The mass ratio of porous graphene is 7:1-9:1；The speed of the high speed ball milling is 400-600rpm, time 8-12h.
10. a kind of application of any negative electrode material of claim 1-3 in negative electrode of lithium ion battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111916674A (en) * | 2020-08-04 | 2020-11-10 | 珠海冠宇电池股份有限公司 | Negative plate, preparation method and battery |
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Application publication date: 20190625 |