CN108878831A - A method of improving silicon based anode material electric conductivity - Google Patents
A method of improving silicon based anode material electric conductivity Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y02E60/10—Energy storage using batteries
Abstract
A method of improving silicon based anode material electric conductivity, the invention discloses a kind of methods for improving silicon based anode material electric conductivity, the present invention problem unstable for carbon coating layer, using Ti-O-Si chemical bond is formed between the oxygen and silicon particle in titanium oxide, a kind of method for improving silicon based anode material cyclical stability is provided：Titanium oxide is coated on silicon based anode material, the mass fraction of titanium oxide is about 2 ~ 50% after cladding.The beneficial effects of the present invention are：Since the combination of Ti-O key and Si-O key can be all very high, titanium oxide clad is firmly bonded in silicon particle surface, even if undergoing huge volume change, will not fall off from silicon particle surface.And since titanium oxide is semiconductor, conductivity is regulated and controled by defect, and titanium dioxide is converted to the titanium oxide of anoxic using the reproducibility of silicon, can effectively improve the electric conductivity of titanium oxide clad, the final electric conductivity for improving silicon based anode material.
Description
Technical field
The invention discloses a kind of methods for improving silicon based anode material electric conductivity, belong to electrochemistry and new energy materials neck
Domain.
Background technique
Lithium ion battery is widely used in hand with excellent properties such as its high voltage, high-energy density and long circulation lifes
Machine and Notebook Battery, power battery and energy-storage battery etc..Wherein mobile phone and Notebook Battery are accounted for by lithium ion battery completely
According to because other kinds of battery is unable to reach the rigors of these portable intelligent devices at all.With lithium ion battery
Technology development, shared ratio is also increasing in power battery energy-storage battery, for current development trend, lithium from
Sub- battery is in a rapid development stage, has a extensive future.
With the increasing of smart phone and the lightening of laptop, multifunction and screen, existing lithium-ion electric
Pond is equally difficult to meet the consumer electronics product requirement increasingly harsh to battery, and there is an urgent need to new techniques to effectively improve lithium
The specific energy of ion battery.Lithium ion battery generally include the big critical material of cathode, diaphragm, electrolyte, anode etc. four and other
Auxiliary material, and in four big critical materials, cathode and anode are its core materials, the specific capacity of cathode and positive electrode and embedding de-
Lithium voltage determines the specific energy of lithium ion battery.The common positive electrode of lithium ion battery has cobalt acid lithium, LiMn2O4, three at present
Member and LiFePO4, specific capacity is between 100 ~ 200mAh/g；Common negative electrode material is carbons negative electrode material, and specific capacity exists
Between 250 ~ 360mAh/g.The raising of lithium ion battery specific energy is primarily limited to the specific capacity of positive electrode at present, by each
State scientist effort in more than 20 years, although developing the solid solution cathode material that specific capacity reaches 200 ~ 300mAh/g, by
, temporarily can not be commercial in not yet overcoming its inherent shortcoming, the specific capacity of commercial positive electrode still is below 200 mAh/g.
In the case where the promotion of positive electrode specific capacity is obstructed, the specific capacity for improving negative electrode material is to improve battery specific energy
One of effective way.Current commercialized lithium ion battery mainly uses graphite negative electrodes material, since the theory of graphite is embedding
Lithium capacity is only 372mAh/g, and the material of practical application has reached 360mAh/g, thus such material on capacity almost
Without room for promotion.In order to improve the specific energy of lithium ion battery, the cathode material of various novel height ratio capacities and high rate capability
Material is developed, including silicon substrate, tinbase, nano-carbon material and metal oxide, and wherein silica-base material is due to highest
Specific discharge capacity and lower voltage platform（The theoretical specific capacity of silicon is 4200 mAh/g, and taking off lithium platform voltage is 0.4V）It forms
Lead to electric work however, silicon based anode material along with serious volume expansion and is shunk during embedding de- lithium for research hotspot
The powder of detached and solid electrolyte film of property substance（Solid electrolyte interphase, SEI film）Continuous shape
At, the problems such as directly resulting in specific capacity rapid decay and low efficiency for charge-discharge, in addition, elemental silicon is semiconductor, conductivity is lower,
The electronics transfer being unfavorable in discharge and recharge reaction.
For the above problem of silicon based anode material, the microstructure for optimizing silicon based anode material itself is a kind of essence
Solution.In order to improve the electric conductivity of silicon based anode material, most common method is carbon coating, this is because carbon material is led
Electrical property is moderate, stability is good, cost of material is low and method for coating is more, and still, the binding force between carbon coating layer and silicon particle is weaker,
Due to the huge volume change of silicon particle during embedding de- lithium, carbon coating layer fragmentation is easy to cause to fall off, to reduce material
The electric conductivity of material finally causes the decaying of specific capacity.
Summary of the invention
The present invention problem unstable for above-mentioned carbon coating layer, forms Ti- using between the oxygen and silicon particle in titanium oxide
O-Si chemical bond provides a kind of method for improving silicon based anode material cyclical stability.Technical scheme is as follows：
A method of improving silicon based anode material electric conductivity, the method is：Titanium oxide is coated on silicon based anode material,
The mass fraction of titanium oxide is about 2 ~ 50% after cladding, and preferable range is 5 ~ 20%.
The method and step of first improvement silicon based anode material electric conductivity is as follows（Gas phase cladding）：The silicon substrate is born
Pole material is placed in the atmosphere of titanium tetrachloride exposure a period of time, while being passed through air and vapor is coated, and utilizes silicon substrate
The water of negative electrode material adsorption and the hydroxyl absorption titanium tetrachloride on silicon materials surface are simultaneously hydrolyzed into titanium oxide, can pass through control
The hydrolysis degree of the intake control titanium tetrachloride of humid air and then the control for realizing coated by titanium dioxide amount, being sufficiently stirred makes respectively
Kind powder lot dispersing is uniform.It uniformly heats up under inert atmosphere protection after being covered to complete, keeps the temperature 0.5 ~ 12 hour in 200 ~ 900 DEG C.
Preferred condition be 300 ~ 600 DEG C heat preservation 1-4 hours.
The method and step of second improvement silicon based anode material electric conductivity is as follows（Liquid phase coating method）：By silicon based anode material
Dispersion in a solvent, adds titanium source, and stirring makes solution absorb moisture and hydrolysis in air, filtration drying after the completion of hydrolysis,
Obtained product uniformly heats up under inert atmosphere protection, in 200 ~ 900 DEG C keep the temperature 0.5 ~ 12 hour, preferred condition be
1 ~ 4 hour is kept the temperature at 300 ~ 600 DEG C.
Preferably, the titanium source is the titanium salt of facile hydrolysis.
It is furthermore preferred that the titanium salt is titanium tetrachloride, butyl titanate and/or ammonium titanium fluoride.
In two methods of above-mentioned offer, the silicon based anode material includes simple substance silicon particle, porous silicon, nanometer
SiO after silicon, SiO and disproportionation.TiO after cladding2Mass fraction be about 2 ~ 50%, preferable range is 5 ~ 20%.
Principle is to coat layer of titanium dioxide on silica-base material surface, is then heat-treated at a certain temperature, utilizes silicon
Coated by titanium dioxide layer is transformed into the anoxic titanium oxide clad of high conductivity by reproducibility, and due to titanium oxide clad and
Powerful chemical key between silicon particle, the clad is very secured, will not fall off in embedding de- lithium circulation, to effectively improve silicon substrate
The cyclical stability of negative electrode material.
The beneficial effects of the present invention are：Since the combination of Ti-O key and Si-O key can be all very high, titanium-oxide-coated
Layer is firmly bonded in silicon particle surface, even if undergoing huge volume change, will not fall off from silicon particle surface.And due to
Titanium oxide is semiconductor, and conductivity is regulated and controled by defect, and titanium dioxide is converted to the titanium oxide of anoxic using the reproducibility of silicon,
The electric conductivity of titanium oxide clad can be effectively improved, the final electric conductivity for improving silicon based anode material.
Specific embodiment
Embodiment one
1, coated by titanium dioxide layer is made：By elemental silicon powder（1 micron of average grain diameter）It is placed in the glass tube of Rotary Evaporators,
Carrier gas is done by TiCl with argon gas4Steam is brought into glass tube, while being passed through humid air（Humidity is between 10%-60%, gas velocity
Rate is in 50-200 mL/min）, glass tube keep rotation, ventilation 5 hours after close, take out sample.
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 200 DEG C of heat preservations per minute
12 hours, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300 mA/g, measures its embedding lithium capacity for the first time
For 3127mAh/g, first charge discharge efficiency 57%, specific capacity is 359mAh/g after recycling 100 times；As a comparison, original elemental silicon powder
Embedding lithium capacity is 2433mAh/g for the first time, and first charge discharge efficiency 34%, specific capacity is 132mAh/g after recycling 100 times.
Embodiment two
1, coated by titanium dioxide layer is made：By porous silicon powder（3 microns of average grain diameter, 120 m of specific surface area2/g）It is placed on rotation
In the glass tube of evaporimeter, carrier gas is done by TiCl with argon gas4Steam is brought into glass tube, while being passed through humid air, and glass tube is protected
Rotation is held, ventilation is closed after 6 hours, takes out sample.
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 500 DEG C of heat preservations per minute
2 hours, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300mA/g, measures its embedding lithium capacity for the first time
For 3347mAh/g, first charge discharge efficiency 77%, specific capacity is 1564mAh/g after recycling 100 times；As a comparison, original porous silicon powder
Embedding lithium capacity is 1974mAh/g to material for the first time, and first charge discharge efficiency 64%, specific capacity is 1042mAh/g after recycling 100 times.
Embodiment three
1, coated by titanium dioxide layer is made：By nano-silicon powder（Average grain diameter 100nm）It is placed in the glass tube of Rotary Evaporators,
Carrier gas is done by TiCl with argon gas4Steam is brought into glass tube, while being passed through humid air, and glass tube keeps rotation, is ventilated 12 hours
After close, take out sample.
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 300 DEG C of heat preservations per minute
4 hours, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300 mA/g, measures its embedding lithium capacity for the first time
For 3521mAh/g, first charge discharge efficiency 71%, specific capacity is 1232mAh/g after recycling 100 times；As a comparison, original nano silica fume
Embedding lithium capacity is 3274mAh/g to material for the first time, and first charge discharge efficiency 65%, specific capacity is 646mAh/g after recycling 100 times.
Example IV
1, coated by titanium dioxide layer is made：By SiO powder（5 microns of average grain diameter）It is placed in the glass tube of Rotary Evaporators, uses
Argon gas does carrier gas for TiCl4Steam is brought into glass tube, while being passed through humid air, and glass tube keeps rotation, and ventilation is closed after 2 hours
It closes, takes out sample.
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 900 DEG C of heat preservations per minute
0.5 hour, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300 mA/g, measures its embedding lithium capacity for the first time
For 1812mAh/g, first charge discharge efficiency 63%, specific capacity is 456mAh/g after recycling 100 times；As a comparison, original SiO material end is first
Secondary embedding lithium capacity is 1367mAh/g, and first charge discharge efficiency 57%, specific capacity is 235mAh/g after recycling 100 times.
Embodiment five
1, coated by titanium dioxide layer is made：By the SiO powder after disproportionation（2 microns of average grain diameter）It is placed on the glass of Rotary Evaporators
Guan Zhong does carrier gas with argon gas and bring TiCl4 steam in glass tube into, while being passed through humid air, and glass tube keeps rotation, ventilation 3
It is closed after hour, takes out sample.
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 500 DEG C of heat preservations per minute
4 hours, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300mA/g, measures its embedding lithium capacity for the first time
For 1541mAh/g, first charge discharge efficiency 75%, specific capacity is 923mAh/g after recycling 100 times；As a comparison, original disproportionation SiO powder
Embedding lithium capacity is 1348mAh/g to material for the first time, and first charge discharge efficiency 62%, specific capacity is 595mAh/g after recycling 100 times.
Embodiment six
1, coated by titanium dioxide layer is made：In beaker by nano-silicon powder（Average grain diameter 100nm）It is dispersed in n-hexane, instills
TiCl4, stirring are closed after one day, take out sample, since TiCl4 almost all hydrolyzes, can control nano-silicon and TiCl4
Additional amount control content of titanium dioxide, wherein than range, the TiCl4 in 4.6%-70%, this example adds the added quality of TiCl4
Entering amount is 46%, and preparation-obtained content of titanium dioxide is 20%.
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 600 DEG C of heat preservations per minute
4 hours, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300mA/g, measures its embedding lithium capacity for the first time
For 2640mAh/g, first charge discharge efficiency 78%, specific capacity is 1232mAh/g after recycling 100 times；As a comparison, original nano silica fume
Embedding lithium capacity is 3274mAh/g to material for the first time, and first charge discharge efficiency 65%, specific capacity is 646mAh/g after recycling 100 times.
Embodiment seven
1, coated by titanium dioxide layer is made：In beaker by the SiO powder after disproportionation（2 microns of average grain diameter）In disperse water, instill
Ammonium titanium fluoride, stirring are closed after one day, take out sample, since ammonium titanium fluoride almost all hydrolyzes, can control nano-silicon
Content of titanium dioxide is controlled with the additional amount of ammonium titanium fluoride, content of titanium dioxide is 5% in this example.
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 450 DEG C of heat preservations per minute
4 hours, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300mA/g, measures its embedding lithium capacity for the first time
For 1655mAh/g, first charge discharge efficiency 76%, specific capacity is 821mAh/g after recycling 100 times；As a comparison, original disproportionation SiO powder
Embedding lithium capacity is 1348mAh/g to material for the first time, and first charge discharge efficiency 62%, specific capacity is 595mAh/g after recycling 100 times.
Embodiment eight
1, coated by titanium dioxide layer is made：In beaker by SiO powder（5 microns of average grain diameter）Dispersion in ethanol, instills metatitanic acid
Four butyl esters, stirring are closed after one day, take out sample, since butyl titanate almost all hydrolyzes, can control nano-silicon
Content of titanium dioxide is controlled with the additional amount of butyl titanate, content of titanium dioxide is 2% in this example.
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 450 DEG C of heat preservations per minute
4 hours, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300 mA/g, measures its embedding lithium capacity for the first time
For 1912mAh/g, first charge discharge efficiency 66%, specific capacity is 657mAh/g after recycling 100 times；As a comparison, original SiO material end is first
Secondary embedding lithium capacity is 1367mAh/g, and first charge discharge efficiency 57%, specific capacity is 235mAh/g after recycling 100 times.
Embodiment nine
1, coated by titanium dioxide layer is made：In beaker by porous silicon powder（3 microns of average grain diameter, 120 m2/g of specific surface area）Point
It dissipating in ethanol, instills butyl titanate, stirring is closed after one day, sample is taken out, since butyl titanate almost all hydrolyzes,
Therefore it can control the additional amount of nano-silicon and butyl titanate to control content of titanium dioxide, content of titanium dioxide is in this example
50%。
2, it is heat-treated：Above-mentioned sample is transferred in the stove of inert atmosphere protection, 10 DEG C are warming up to 450 DEG C of heat preservations per minute
4 hours, take out to obtain finished product.
3, electrochemical property test：By above-mentioned silicon based anode material, acetylene black and LA133 binder according to 80:10:10
It is combined uniform slurry, is coated on copper foil, dry, punching is assembled into button cell, wherein being lithium metal to electrode
Piece, electrolyte are general lithium-ion battery electrolytes, and the electric current of charge-discharge test is 300mA/g, measures its embedding lithium capacity for the first time
For 1569mAh/g, first charge discharge efficiency 69%, specific capacity is 1023mAh/g after recycling 100 times；As a comparison, original porous silicon powder
Embedding lithium capacity is 1974mAh/g to material for the first time, and first charge discharge efficiency 64%, specific capacity is 1042mAh/g after recycling 100 times.
Claims (8)
1. a kind of method for improving silicon based anode material electric conductivity, which is characterized in that the method is：Using gas phase cladding
Or liquid phase coating method coats titanium oxide on silicon based anode material, mass fraction shared by the titanium oxide of cladding is about 2 ~ 50%.
2. improving the method for silicon based anode material electric conductivity as described in claim 1, which is characterized in that the gas phase cladding
Method includes the following steps, namely：The silicon based anode material is placed in the atmosphere of titanium tetrachloride, while being passed through humid air progress
Cladding, uniformly heats up under inert atmosphere protection after being covered to complete, keeps the temperature 0.5 ~ 12 hour at 200 ~ 900 DEG C.
3. improving the method for silicon based anode material electric conductivity as claimed in claim 2, which is characterized in that be passed through humid air
Humidity range is 10%-60%, and for airflow rate between 50-200 mL/min, the post-processing approach that is covered to complete is at 300 ~ 600 DEG C
Heat preservation 1-4 hours.
4. improving the method for silicon based anode material electric conductivity as described in claim 1, which is characterized in that the liquid phase coating
Method includes the following steps, namely：In a solvent by silicon based anode material dispersion, titanium source is added, stirring makes its hydrolysis, and hydrolysis is completed
Filtration drying afterwards, obtained product uniformly heat up under inert atmosphere protection, keep the temperature 0.5 ~ 12 hour in 200 ~ 900 DEG C.
5. improving the method for silicon based anode material electric conductivity as claimed in claim 4, which is characterized in that it is described, it obtains
Product uniformly heats up under inert atmosphere protection, keeps the temperature 1-4 hours at 300 ~ 600 DEG C.
6. improving the method for silicon based anode material electric conductivity as claimed in claim 4, which is characterized in that the titanium source is easy
The titanium salt of hydrolysis.
7. improving the method for silicon based anode material electric conductivity as claimed in claim 5, which is characterized in that the titanium salt is
TiCl4, butyl titanate and/or ammonium titanium fluoride.
8. such as the method as claimed in any one of claims 1 to 7 for improving silicon based anode material electric conductivity, which is characterized in that
The silicon based anode material includes the SiO after elemental silicon, porous silicon, nano-silicon, SiO and disproportionation.
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| YING BAI等: ""Core-shell Si@TiO2 nanosphere anode by atomic layer deposition for Li-ion batteries"", 《JOURNAL OF POWER SOURCES 》 * |
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