CN106207145B - A kind of silicium cathode active material and preparation method thereof and silene lithium battery obtained - Google Patents
A kind of silicium cathode active material and preparation method thereof and silene lithium battery obtained Download PDFInfo
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- CN106207145B CN106207145B CN201610850378.XA CN201610850378A CN106207145B CN 106207145 B CN106207145 B CN 106207145B CN 201610850378 A CN201610850378 A CN 201610850378A CN 106207145 B CN106207145 B CN 106207145B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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 field of batteries, in particular to a kind of silicium cathode active material and preparation method thereof and silene lithium battery obtained.A kind of silicium cathode active material, by heating melting is made under inert gas conditions after the mixing of following raw material: by weight, 100-150 parts of silicon source, 10-50 parts of graphene substance, 3-8 parts of borax, 1-5 parts of Nd, 1-5 parts of Ge, 2-7 parts of Sb, 3-8 parts of Se, 1-3 parts of Bi.Silicium cathode active material provided by the invention, it is screened by test of many times, using silicon source and graphene substance as primary raw material, again by adding the elements such as certain borax and Nd, Ge, Sb, the active material performance made of melting is stablized, manufactured battery specific capacity with higher, charging time significantly reduces, discharge time significantly extends, and manufactured battery, through survivable in multiple charge and discharge process, electrochemical cycle stability significantly improves.
Description
Technical field
The present invention relates to field of batteries, in particular to a kind of silicium cathode active material and preparation method thereof and are made
Silene lithium battery.
Background technique
Lithium ion battery have energy density is high, energy efficiency is high, have extended cycle life, memory-less effect, repid discharge, from
Discharge rate is low, operating temperature range is wide and it is safe and reliable the advantages that, thus become countries in the world scientist make great efforts research it is important
Direction.
The theoretical energy storage density that silicon materials do negative electrode material is up to 4200mAh/g, is energy storage density in all negative electrode materials
It is highest, far super present commercial graphite negative electrode.
The energy density that battery actually can be realized is substantially less than the theoretical energy density calculated based on active material.It is right
This problem is particularly acute for silicon cathode lithium ion battery, this is because in charge and discharge cycles, since lithium ion is continuous
Ground insertion and abjection, the volume change of silicon can achieve 400%, thus can lead to the problem of a series of, silicon particle crushing and material
The fracture of material can destroy electrode structure, so that conductive be deteriorated causes capacity to decline, in electrochemistry cyclic process, along thickness of electrode side
To electrochemical reaction caused by unevenly polarization will lead to electrode stratiform rupture and removing occur, and then there is conductive network and collapse
Routed and electrode failure.Simultaneously because volume volume change during deintercalation and insertion lithium ion is excessive, lead to electrode table
The SEI film in face constantly generates and breakage, as a result can SEI is continuously increased, and active material is consumed, so that under the capacity of battery
Drop, influences the service life of battery.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of silicium cathode active material for lithium ion battery, silicium cathode work
Property physical property stablize, substantially without breakage after being used for a long time.
The second object of the present invention is to provide the preparation method of silicium cathode active material described in one kind, and this method is simple
It is easy, silicium cathode active material superior performance obtained.
The third object of the present invention is to provide a kind of silicium cathode for lithium ion battery, by by above-mentioned silicium cathode
Active material is mixed with specific binder, further increases the stability of silicium cathode active material performance.
The fourth object of the present invention is to provide a kind of silene lithium ion battery, and the battery charge time is short, discharge time
It is long, good cycling stability.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of silicium cathode active material, by heating melting is made under inert gas conditions after the mixing of following raw material: by weight
It measures part to count, 100-150 parts of silicon source, 10-50 parts of graphene substance, 3-8 parts of borax, 1-5 parts of Nd, 1-5 parts of Ge, Sb 2-7
Part, 3-8 parts of Se, 1-3 parts of Bi.
Wherein, Nd is neodymium element, and Ge is Germanium, and Sb is antimony element, and Se is selenium element, and Bi is bismuth element；Graphite alkenes
Substance includes one or more of mixing of graphene, biomass graphene, graphene oxide, Graphene derivative, wherein stone
Black ene derivative includes the graphene of element doping.
Provided by the present invention for the silicium cathode active material of lithium ion battery, screened by test of many times, with silicon source and
Graphene substance is primary raw material, then by adding the elements such as certain borax and Nd, Ge, Sb, made of melting
Active material performance is stablized, manufactured battery specific capacity with higher, and the charging time significantly reduces, and discharge time significantly prolongs
It is long, and manufactured battery, through survivable in multiple charge and discharge process, electrochemical cycle stability significantly improves.
In order to enhance the collaboration reinforcing effect between each raw material, reach more superior comprehensive performance, it is preferable that by weight
Meter, 120-140 parts of silicon source, 30-40 parts of graphene substance, 3-5 parts of borax, 1-2 parts of Nd, 1-2 parts of Ge, 2-3 parts of Sb, Se
3-5 parts, 1-2 parts of Bi.
Inert gas in the present invention includes argon gas, nitrogen etc., wherein with the silicium cathode active matter obtained under condition of nitrogen gas
Matter performance is more superior, it may be possible to as in the high temperature conditions, the nitrogen in nitrogen can be fitted in active material obtained, into
One step increases the stability of silicium cathode active material obtained.
Further, it is any one or more of to include the following three types silicon source for the silicon source；
First silicon source is that silicon powder, silica, silicate are any one or more of；
Second silicon source is methylchlorosilane, phenyl chlorosilane, methylvinyl-chlorosilanes, appointing in vinyl trichlorosilane
It is one or more；
Third silicon source is that silane hydrocarbon, cyclosilane hydrocarbon, dichlorosilane, trichlorosilane are any one or more of.
Different silicon sources has more significant influence to the performance of silicium cathode active material obtained, wherein with three kinds of silicon sources
Mixture, especially the performance of silicium cathode active material obtained is best at a specific ratio.Experiment proves that with three kinds of silicon sources
After mixing, through high-temperature fusion, then pass through cooling gradually, will form a kind of orderly structure, the structure quality between each ingredient
Closely, for making battery cathode, in use, performance is stablized, and through multiple charge-discharge test, structure will not be damaged
Evil, good cycling stability.
Preferably, the silicon source includes three kinds of silicon sources, first silicon source, second silicon source and the third silicon source
Weight ratio is 6-8:3-5:1.
Preferably, the graphene substance also passes through following processing before being melted:
Graphene substance is crushed to 50 μm hereinafter, then handling 3- under the microwave condition of 300-500W power
5min, it is cooling.
By the microwave treatment of certain power, graphene substance is in swelling state, be conducive to it is subsequent in the molten state
It is preferably merged with other substances, increases the order of final active material obtained.
The present invention also provides the preparation methods of above-mentioned silicium cathode active material, comprising the following steps:
After each raw material is mixed, be warming up to 1300-1500 DEG C with the heating rate of 3-5 DEG C/s, keep the temperature 3-5min, then with
The rate of temperature fall of 3-5 DEG C/min is cooled to room temperature.
Each raw material is first rapidly heated to certain temperature by the present invention, then melts at 1300-1500 DEG C, using relatively slow
Cooling down so that abundant consolute between each raw material, and more orderly structure is formed during slow cooling, silicon obtained
Negative electrode active material performance is more stable.Wherein, room temperature refers to that temperature is 15-25 DEG C.
The present invention also provides a kind of silicium cathode for lithium ion battery, including collector, coated on the collector
Following substance: the described in any item silicium cathode active materials of claim 1-4 are milled active material powder obtained, conductive agent
And binder.
The silicium cathode is prepared according to existing silicium cathode.
Due to being added to some elements in the silicium cathode active material in the present invention, silicium cathode active material obtained is less
It is easy to be bonded together, the present inventor is through test of many times, such as hydroxymethyl cellulose, fluoropolymer, third from numerous binders
In the single compositions such as olefine acid ester polymer, polyvinylpyrrolidone, polyvinyl alcohol and multicomponent combination, finally screen to obtain its effect
More preferably binder.
Preferably, the binder is the mixture of hydroxymethyl cellulose, polyvinylpyrrolidone and polyvinyl alcohol；It is described
The additive amount of binder is the 3%-5% of the active material powder weight.
It is highly preferred that the weight ratio of the hydroxymethyl cellulose, the polyvinylpyrrolidone, the polyvinyl alcohol is
2:1-2:0.5-1。
In order to reach better bond effect, and keep active material distribution more uniform, silicium cathode obtained such as charge and discharge,
The comprehensive performances such as stability are more superior, and save the cost, it is preferable that the partial size of the active material be 50 μm hereinafter,
Preferably 5-20 μm.
The present invention also provides a kind of silene lithium ion batteries, including anode, above-mentioned silicium cathode, between positive and negative anodes
Diaphragm and electrolyte；
The active material of the anode is preferably LiFePO4.
Further, the battery is laminated structure, and plus plate current-collecting body is aluminium foil, and negative current collector is copper foil；
As according to demand, the density for the active material being coated on positive and negative anodes collector can be 150-180g/cm2。
Electrolyte is lithium hexafluorophosphate solution, if concentration can be 1M.
Silene lithium ion battery provided by the invention, is prepared using following methods:
Plus plate current-collecting body is aluminium foil, and negative current collector is copper foil；Respectively weigh the active material being coated on positive and negative anodes collector,
Conductive agent Super P and binder, the weight ratio of these three substances are 20-25:1:0.8-1.5；Distilled water, mixing is added
It is slurried, is then respectively coated on positive and negative anodes collector, is rolled after coating, then dried, drying is first in 80-85
DEG C retain 2-3min, then in 100-110 DEG C of reservation 3-5min；Then lamination is carried out, places diaphragm during lamination
Between positive and negative anodes, and inject electrolyte.Diaphragm used is the diaphragm of existing lithium battery, such as high-strength thin-film
The polyolefin porous membrane of change.
Compared with prior art, the invention has the benefit that
(1) silicium cathode active material provided by the invention, using silicon source and graphene substance as primary raw material, then by adding
Add the elements such as certain borax and Nd, Ge, Sb, the active material performance made of melting is stablized, and manufactured battery has
Higher specific capacity, charging time significantly reduce, and discharge time significantly extends.
(2) present invention by limit silicon source type and various silicon sources between proportion, each ingredient after melt process,
It will form a kind of orderly structure, the structure quality is close, and for making battery cathode, in use, performance is stablized, warp
Multiple charge-discharge test, structure will not be damaged, good cycling stability.
(3) present invention certain disposition is also carried out to graphene substance, be conducive to it is subsequent in the molten state with other objects
Matter preferably merges, and increases the order of final active material obtained.
(4) the present invention also provides the preparation methods of silicium cathode active material, by the control of warming and cooling rate, so that respectively
Abundant consolute between raw material, and more orderly structure is formed during slow cooling, it is living to further increase silicium cathode obtained
The stability of property substance performance.
(5) present invention also defines the type of binder and the partial sizes of active material, so that living in silicium cathode obtained
Property component distributing is uniform, and comprehensive performance is more superior.
(6) the present invention also provides a kind of silene lithium ion battery, specific capacity with higher, the charging time significantly drops
Low, discharge time significantly extends, and manufactured battery is through survivable, electrochemical cycle stability in multiple charge and discharge process
Property significantly improves.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
By weight, following raw material is taken:
Group 1: 100 parts of silicon powder, 20 parts of graphene, 2 parts of Nd, 2 parts of Ge, 2 parts of Sb, 3 parts of Se, 1 part of Bi；
Group 2: 100 parts of silicon powder, 20 parts of graphene, 5 parts of borax, 2 parts of Nd, 2 parts of Ge, 2 parts of Sb, 3 parts of Se, 1 part of Bi；
Group 3: 70 parts of silicon powder, 40 parts of vinyl trichlorosilane, 10 parts of dichlorosilane, 20 parts of graphene, 5 parts of borax, Nd 2
Part, 2 parts of Ge, 2 parts of Sb, 3 parts of Se, 1 part of Bi；
3 points of group are two groups of 3-1 groups and 3-2 group, and unlike 3-1 group, the graphene in 3-2 group is in the micro- of 300W power
5min is handled under the conditions of wave；
Each raw material is taken in the raw material weight ratio in group 1-3, after each raw material mixing, with the liter of 3 DEG C/s in nitrogen atmosphere
Warm rate is warming up to 1300 DEG C, keeps the temperature 5min, is then cooled to room temperature with the rate of temperature fall of 3 DEG C/min, obtains silicium cathode activity
Substance.
In experiments it is found that the silicium cathode active material in the present invention is less susceptible to be bonded together, manufactured silicium cathode
It is easily dispersed after active material coating uneven.The present inventor is from numerous binders such as hydroxymethyl cellulose, fluoropolymer
In the single compositions such as object, acrylate polymer, polyvinylpyrrolidone, polyvinyl alcohol and multicomponent combination, screening is bonded
The pretty good binder of effect.Binder is the mixture of hydroxymethyl cellulose, polyvinylpyrrolidone and polyvinyl alcohol, wherein
Hydroxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol weight ratio be 2:1-2:0.5-1 can reach good bonding
Effect, in the present embodiment, selection hydroxymethyl cellulose, polyvinylpyrrolidone, the weight ratio of polyvinyl alcohol are mixed for 2:1:1
Binder made of conjunction, wherein the additive amount of binder is the 3%-5% of active material powder weight.
Silicium cathode active material mills obtained granularity as 50 μm of active material powders below, and positive active material is phosphorus
Sour iron lithium, it is aluminium foil that plus plate current-collecting body, which is selected, and negative current collector is copper foil；Respectively weigh the active matter being coated on positive and negative anodes collector
Matter, conductive agent Super P and binder, the weight ratio of these three substances are 20:1:1；Distilled water is added, is mixed and made into slurry
Then shape is respectively coated on positive and negative anodes collector, is rolled after coating, then dried, drying is first to retain at 80 DEG C
3min, then in 110 DEG C of reservation 5min；Then lamination is carried out, is placed on polyolefin porous membrane during lamination positive and negative
Between pole, and inject the lithium hexafluorophosphate solution electrolyte of 1M.
Control group: according to application No. is a kind of silicon cathode lithium ion battery and manufacturing methods disclosed in 201310706341.6
In embodiment 3 made from battery.
The specific capacity of battery made from different groups is measured, and carries out the test of charging time and discharge time, as a result such as
Shown in table 1.
1 testing result of table
| Parameter | Control group | Group 1 | Group 2 | Group 3-1 | Group 3-2 |
| Specific capacity (mAh/g) | 450 | 800 | 820 | 850 | 850 |
| Charging time | 2h | 30min | 30min | 30min | 25min |
| Discharge time | 2h | 6h | 6h | 6h | 7h |
As it can be seen from table 1 battery made of silicium cathode active material provided by the invention has specific capacity big, charging
Fastly, the feature of discharge time length.
In addition, under the performance for measuring battery made from different groups is stablized, specifically: it is enterprising to be placed on charge-discharge test instrument
Row constant current charge-discharge test carries out specific capacity after charge and discharge 100 times, 200 times, 300 times, 500 times, 700 times and 1000 times respectively
Detection, obtain that the results are shown in Table 2.
2 testing result of table
| Parameter | Control group | Group 1 | Group 2 | Group 3-1 | Group 3-2 |
| 100 specific capacities (mAh/g) of charge and discharge | 450 | 800 | 820 | 850 | 850 |
| 200 specific capacities (mAh/g) of charge and discharge | 380 | 750 | 800 | 850 | 850 |
| 300 specific capacities (mAh/g) of charge and discharge | 200 | 600 | 700 | 810 | 820 |
| 500 specific capacities (mAh/g) of charge and discharge | 100 | 520 | 620 | 770 | 780 |
| 700 specific capacities (mAh/g) of charge and discharge | 50 | 400 | 570 | 680 | 700 |
| 1000 specific capacities (mAh/g) of charge and discharge | - | 250 | 320 | 430 | 450 |
Note: "-" expression does not detect.
From table 2 it can be seen that battery made of silicium cathode active material provided by the invention is steady relative to existing battery
It is qualitative have be obviously improved, especially organize 3 in battery obtained, specific capacity still reaches 50% or more after charge and discharge 1000 times.
Embodiment 2
By weight, following raw material is taken:
Group 1: 90 parts of silica, 45 parts of vinyl trichlorosilane, 15 parts of dichlorosilane, 50 parts of graphene, 8 parts of borax,
5 parts of Nd, 5 parts of Ge, 7 parts of Sb, 8 parts of Se, 3 parts of Bi；
Group 2: 60 parts of silicate, 50 parts of phenyl chlorosilane, 10 parts of dichlorosilane, 30 parts of graphene, 3 parts of borax, 1 part of Nd,
1 part of Ge, 3 parts of Sb, 5 parts of Se, 2 parts of Bi；
Group 3: 80 parts of silica, 50 parts of vinyl trichlorosilane, 10 parts of dichlorosilane, 40 parts of graphene, 5 parts of borax,
2 parts of Nd, 2 parts of Ge, 2 parts of Sb, 3 parts of Se, 1 part of Bi；
Group 4: 80 parts of silicon powder, 40 parts of vinyl trichlorosilane, 10 parts of dichlorosilane, 35 parts of graphene, 4 parts of borax, Nd 2
Part, 2 parts of Ge, 3 parts of Sb, 4 parts of Se, 2 parts of Bi；
Group 5: 70 parts of silica, 20 parts of methylchlorosilane, 10 parts of phenyl chlorosilane, 10 parts of methylvinyl-chlorosilanes,
10 parts of dichlorosilane, 35 parts of graphene, 4 parts of borax, 2 parts of Nd, 2 parts of Ge, 3 parts of Sb, 4 parts of Se, 2 parts of Bi；
Group 6: 40 parts of silicon powder, 30 parts of silica, 40 parts of vinyl trichlorosilane, 5 parts of cyclosilane hydrocarbon, 5 parts of dichlorosilane,
35 parts of graphene, 4 parts of borax, 2 parts of Nd, 2 parts of Ge, 3 parts of Sb, 4 parts of Se, 2 parts of Bi；
Each raw material is taken in the raw material weight ratio in group 1-6, wherein Graphene powder is broken to 50 μm hereinafter, then in 400W
5min is handled under the microwave condition of power, it is cooling；
After each raw material mixing, 1300 DEG C are warming up to the heating rate of 3 DEG C/s in nitrogen atmosphere, keeps the temperature 5min, then
It is cooled to room temperature with the rate of temperature fall of 3 DEG C/min, obtains silicium cathode active material.
Silicium cathode active material mills obtained granularity as 50 μm of active material powders below；Binder is hydroxylmethyl cellulose
Element, polyvinylpyrrolidone, polyvinyl alcohol are with the binder that weight ratio is that 2:1:1 is mixed, the additive amount of binder
The 5% of active material powder weight；
The active material of anode is LiFePO4, and it is aluminium foil that plus plate current-collecting body, which is selected, and negative current collector is copper foil；Respectively weigh
Active material, conductive agent Super P and the binder being coated on positive and negative anodes collector, the weight ratio of these three substances are
20:1:1；Distilled water is added, is mixed and made into pulpous state, is then respectively coated on positive and negative anodes collector, is rolled after coating, so
After dry, drying be first in 80 DEG C of reservation 3min, then in 110 DEG C of reservation 5min；Then lamination is carried out, during lamination
Polyolefin porous membrane is placed between positive and negative anodes, and injects the lithium hexafluorophosphate solution electrolyte of 1M.
The specific capacity of battery made from different groups is measured, and carries out the test of charging time and discharge time, as a result such as
Shown in table 3.
3 testing result of table
From table 3 it can be seen that battery made of silicium cathode active material provided by the invention has specific capacity big, charging
Fastly, the feature of discharge time length.
In addition, under the performance for measuring battery made from different groups is stablized, specifically: it is enterprising to be placed on charge-discharge test instrument
Row constant current charge-discharge test carries out the detection of specific capacity, obtains after distinguishing charge and discharge 100 times, 300 times, 500 times and 1000 times
The results are shown in Table 4.
4 testing result of table
| Parameter | Group 1 | Group 2 | Group 3 | Group 4 | Group 5 | Group 6 |
| 100 specific capacities (mAh/g) of charge and discharge | 845 | 850 | 855 | 855 | 860 | 860 |
| 300 specific capacities (mAh/g) of charge and discharge | 815 | 820 | 825 | 823 | 827 | 828 |
| 500 specific capacities (mAh/g) of charge and discharge | 775 | 780 | 780 | 785 | 790 | 790 |
| 1000 specific capacities (mAh/g) of charge and discharge | 440 | 450 | 455 | 450 | 465 | 470 |
It is obviously improved from table 4, it can be seen that stability test made of silicium cathode active material provided by the invention has,
Specific capacity still reaches 50% or more after charge and discharge 1000 times.
Embodiment 3
By weight, following raw material is taken:
40 parts of silicon powder, 30 parts of silica, 40 parts of vinyl trichlorosilane, 5 parts of cyclosilane hydrocarbon, 5 parts of dichlorosilane, graphite
35 parts of alkene, 4 parts of borax, 2 parts of Nd, 2 parts of Ge, 3 parts of Sb, 4 parts of Se, 2 parts of Bi；
Each raw material is taken in the above raw material weight ratio, wherein Graphene powder is broken to 50 μm hereinafter, then in 500W power
3min is handled under microwave condition, it is cooling；
After each raw material mixing, 1500 DEG C are warming up to the heating rate of 5 DEG C/s in nitrogen atmosphere, keeps the temperature 3min, then
It is cooled to room temperature with the rate of temperature fall of 5 DEG C/min, obtains silicium cathode active material.
Silicium cathode active material mills obtained granularity as 5-20 μm of active material powder, and binder is hydroxylmethyl cellulose
Element, polyvinylpyrrolidone, polyvinyl alcohol are with the binder that weight ratio is that 2:2:1 is mixed, the additive amount of binder
The 3% of active material powder weight；
The active material of anode is LiFePO4, and it is aluminium foil that plus plate current-collecting body, which is selected, and negative current collector is copper foil；Respectively weigh
Active material, conductive agent Super P and the binder being coated on positive and negative anodes collector, the weight ratio of these three substances are
20:1:1；Distilled water is added, is mixed and made into pulpous state, is then respectively coated on positive and negative anodes collector, is rolled after coating, so
After dry, drying be first in 80 DEG C of reservation 3min, then in 110 DEG C of reservation 5min；Then lamination is carried out, during lamination
Polyolefin porous membrane is placed between positive and negative anodes, and injects the lithium hexafluorophosphate solution electrolyte of 1M.
The specific capacity of battery made from different groups is measured, and carries out charging time, the test of discharge time and battery
Performance stablize, it is as a result consistent with 2 group of 6 result of embodiment.
Embodiment 4
By weight, following raw material is taken:
40 parts of silicon powder, 30 parts of silica, 40 parts of vinyl trichlorosilane, 5 parts of cyclosilane hydrocarbon, 5 parts of dichlorosilane, graphite
35 parts of alkene, 4 parts of borax, 2 parts of Nd, 2 parts of Ge, 3 parts of Sb, 4 parts of Se, 2 parts of Bi；
Each raw material is taken in the above raw material weight ratio, wherein Graphene powder is broken to 50 μm hereinafter, then in 300W power
5min is handled under microwave condition, it is cooling；
After each raw material mixing, 1400 DEG C are warming up to the heating rate of 4 DEG C/s in nitrogen atmosphere, keeps the temperature 5min, then
It is cooled to room temperature with the rate of temperature fall of 4 DEG C/min, obtains silicium cathode active material.
Silicium cathode active material mills obtained granularity as 5-20 μm of active material powder, and binder is hydroxylmethyl cellulose
Element, polyvinylpyrrolidone, polyvinyl alcohol are with the binder that weight ratio is that 2:2:0.5 is mixed, the additive amount of binder
It is the 3% of active material powder weight；
The active material of anode is LiFePO4, and it is aluminium foil that plus plate current-collecting body, which is selected, and negative current collector is copper foil；Respectively weigh
Active material, conductive agent Super P and the binder being coated on positive and negative anodes collector, the weight ratio of these three substances are
20:1:1；Distilled water is added, is mixed and made into pulpous state, is then respectively coated on positive and negative anodes collector, is rolled after coating, so
After dry, drying be first in 80 DEG C of reservation 3min, then in 110 DEG C of reservation 5min；Then lamination is carried out, during lamination
Polyolefin porous membrane is placed between positive and negative anodes, and injects the lithium hexafluorophosphate solution electrolyte of 1M.
The specific capacity of battery made from different groups is measured, and carries out charging time, the test of discharge time and battery
Performance stablize, it is as a result consistent with 2 group of 6 result of embodiment.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (11)
1. a kind of silicium cathode active material for lithium ion battery, which is characterized in that in nitrogen item after being mixed by following raw material
Heating melting is made under part: by weight, 100-150 parts of silicon source, 10-50 parts of graphene substance, 3-8 parts of borax, Nd 1-
5 parts, 1-5 parts of Ge, 2-7 parts of Sb, 3-8 parts of Se, 1-3 parts of Bi；
The silicon source includes the following three types silicon source；
First silicon source is that silicon powder, silica, silicate are any one or more of；
Second silicon source is any one of methylchlorosilane, phenyl chlorosilane, methylvinyl-chlorosilanes, vinyl trichlorosilane
Or it is a variety of；
Third silicon source is that silane hydrocarbon, cyclosilane hydrocarbon, dichlorosilane, trichlorosilane are any one or more of；
The weight ratio of first silicon source, second silicon source and the third silicon source is 6-8:3-5:1；
The graphene substance also passes through following processing before being melted:
Graphene substance is crushed to 50 μm hereinafter, then handle 3-5min under the microwave condition of 300-500W power, it is cold
But；
The silicium cathode active material is prepared by the following method:
After each raw material is mixed, it is warming up to 1300-1500 DEG C with the heating rate of 3-5 DEG C/s, 3-5min is kept the temperature, then with 3-5
DEG C/rate of temperature fall of min is cooled to room temperature.
2. silicium cathode active material according to claim 1, which is characterized in that by weight, 120-140 parts of silicon source,
30-40 parts of graphene substance, 3-5 parts of borax, 1-2 parts of Nd, 1-2 parts of Ge, 2-3 parts of Sb, 3-5 parts of Se, 1-2 parts of Bi.
3. the preparation method of the described in any item silicium cathode active materials of claim 1-2, which is characterized in that including following step
It is rapid:
After each raw material is mixed, it is warming up to 1300-1500 DEG C with the heating rate of 3-5 DEG C/s, 3-5min is kept the temperature, then with 3-5
DEG C/rate of temperature fall of min is cooled to room temperature.
4. a kind of silicium cathode for lithium ion battery, which is characterized in that including collector, following object is coated on the collector
Matter: the described in any item silicium cathode active materials of claim 1-2 are milled active material powder, conductive agent and bonding obtained
Agent.
5. silicium cathode according to claim 4, which is characterized in that the binder is hydroxymethyl cellulose, polyethylene pyrrole
The mixture of pyrrolidone and polyvinyl alcohol, the additive amount of the binder are the 3%-5% of the active material powder weight.
6. silicium cathode according to claim 5, which is characterized in that the hydroxymethyl cellulose, the polyvinylpyrrolidine
Ketone, the polyvinyl alcohol weight ratio be 2:1-2:0.5-1.
7. silicium cathode according to claim 6, which is characterized in that the partial size of the active material is 50 μm or less.
8. silicium cathode according to claim 7, which is characterized in that the partial size of the active material is 5-20 μm.
9. a kind of silene lithium ion battery, which is characterized in that including anode, the described in any item silicium cathodes of claim 4-8, position
Diaphragm and electrolyte between positive and negative anodes.
10. silene lithium ion battery according to claim 9, which is characterized in that the active material of the anode is phosphoric acid
Iron lithium.
11. silene lithium ion battery according to claim 9, which is characterized in that the battery is laminated structure, anode
Collector is aluminium foil, and negative current collector is copper foil.
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| CN101420025A (en) * | 2007-10-26 | 2009-04-29 | 索尼株式会社 | Negative electrode and its manufacturing method, and secondary cell |
| CN101740766A (en) * | 2008-11-21 | 2010-06-16 | 比亚迪股份有限公司 | Cathode active material, preparation method thereof and lithium battery using same |
| CN103996826A (en) * | 2013-02-15 | 2014-08-20 | 三星Sdi株式会社 | Negative active material, and negative electrode and lithium battery each including the negative active material |
| CN203794630U (en) * | 2014-04-04 | 2014-08-27 | 厦门凯纳石墨烯技术有限公司 | Industrial device for continuously producing graphene powder |
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| CN101420025A (en) * | 2007-10-26 | 2009-04-29 | 索尼株式会社 | Negative electrode and its manufacturing method, and secondary cell |
| CN101740766A (en) * | 2008-11-21 | 2010-06-16 | 比亚迪股份有限公司 | Cathode active material, preparation method thereof and lithium battery using same |
| CN103996826A (en) * | 2013-02-15 | 2014-08-20 | 三星Sdi株式会社 | Negative active material, and negative electrode and lithium battery each including the negative active material |
| CN203794630U (en) * | 2014-04-04 | 2014-08-27 | 厦门凯纳石墨烯技术有限公司 | Industrial device for continuously producing graphene powder |
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