CN107293701A - A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole - Google Patents
A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole Download PDFInfo
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- CN107293701A CN107293701A CN201610204053.4A CN201610204053A CN107293701A CN 107293701 A CN107293701 A CN 107293701A CN 201610204053 A CN201610204053 A CN 201610204053A CN 107293701 A CN107293701 A CN 107293701A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
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- 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
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- 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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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 proposes a kind of lithium ion battery anode active material and preparation method thereof and battery, and the negative active core-shell material is core shell structure, and the core includes Li-Si alloy particle, and the shell is carbon-coating；Core is used in the present invention for the negative active core-shell material of core shell structure that Li-Si alloy particle, shell are carbon-coating, the Volumetric expansion occurred when silicon is used as negative pole can effectively be alleviated, it is applied to battery, obtained battery can not only maintain higher capacity, meanwhile, also with good cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole.
Background technology
In the prior art, as lithium ion battery anode active material, the actual capacity of graphite oneself close to the mAh/g of theoretical value 372, but it still can not meet high request of the electrokinetic cell to specific capacity and energy density；And the theoretical capacity of silicon is up to 4212 mAh/g, therefore it is received significant attention in field of lithium ion battery in recent years；The embedding lithium mechanism of silicon is alloying mechanism, and theoretical capacity calculates it in final embedding lithium state（Li22Si5）When volumetric expansion be original 400%, the problem of due to there is volumetric expansion, therefore, when being used as negative active core-shell material, the efflorescence of negative material can be seriously caused to crush, while negative terminal surface SEI films also can be destroyed and regenerated therewith, the expansion for eventually resulting in pole piece further increases, so as to cause electrode capacity significantly to be decayed, cycle performance of battery extreme difference.
In order to solve the system expansion issues of silicon, make the battery prepared that there is preferable cycle performance, prior art in carbon material mainly by adding a small amount of（3~10%）Silica flour, silicon monoxide powder or silicon alloy material, although the specific capacity of negative material can be brought up to 400 ~ 450mAh/g by this method, but the first charge-discharge efficiency of material can decline, and if the Capacity design of negative pole negative material is to more than 600mAh/g, then need the silicon of addition more than 20%, so not only substantially reduce material first charge-discharge efficiency, there is serious volumetric expansion in the substantial amounts of silicon materials of addition, the destruction and material that pole piece conductive network can be caused come off from collector, so as to cause cycle performance of battery poor, can not meet it is practical the need for.
The content of the invention
In order to solve the above-mentioned technical problem the application, proposes a kind of lithium ion battery anode active material, and the negative active core-shell material is core shell structure, and the core includes Li-Si alloy particle, and the shell is carbon-coating.
The present invention also provides a kind of preparation method of lithium ion battery anode active material, including：
(1) carbon source presoma, Li-Si alloy particle powder are mixed and disperseed with organic solvent, obtain slurries；
(2) removal organic solvent is dried in the slurries in step (1), obtains the presoma that carbon source presoma coats Li-Si alloy alloying pellet；
(3) presoma in step (2) is placed under inert atmosphere and be sintered, obtain the lithium ion battery anode active material that core is Li-Si alloy particle, shell is carbon-coating.
The present invention further provides a kind of negative electrode of lithium ion battery, the negative pole includes the lithium ion battery anode active material that the application is proposed.
The present invention proposes a kind of lithium ion battery, and the battery includes above-mentioned negative electrode of lithium ion battery.
In lithium ion battery, because the intercalation potential of the silicon as negative active core-shell material is higher than the intercalation potential of carbon material, therefore, in the charge and discharge process of battery, lithium ion can preferentially be embedded in silicon materials, so as to cause silicon to occur, when " full charge " occurs in silicon, silicon volumetric expansion is up to about 400%, seriously reduces the capacity and cycle performance of battery；Present inventor accidentally in find, use core for the negative active core-shell material of core shell structure that Li-Si alloy particle, shell are carbon-coating, can effectively prevent silicon materials from occurring serious Volumetric expansion caused by " full charge " when being used as negative pole；Speculate its reason, it is probably because in the Li-Si alloy particle that the application is provided, silicon materials have been " embedded " part lithium in itself, thus as cell negative electrode material in use, in the charge and discharge process of battery, the further embedded caused volumetric expansion of lithium is smaller, when de- lithium, lithium in original Li-Si alloy particle can also be deviate from the lump, to keep the high power capacity of battery, while can also alleviate the Volumetric expansion occurred when silicon is used as negative pole；In addition, the presence of Li-Si alloy particle surface carbon shell, Li-Si alloy particle and electrolyte can not only be separated, ensure its stability, topmost, the presence of the carbon shell, inner nuclear material can be coordinated to play more preferable electric conductivity, the part lithium being " embedded " in itself in Li-Si alloy particle simultaneously can maintain void structure one by one during deviating from the later stage, and the void structure can accommodate caused volumetric expansion during embedding lithium next time, therefore further alleviate the Volumetric expansion of negative pole；Negative active core-shell material proposed by the present invention is applied to battery, obtained battery can not only maintain higher capacity, simultaneously, negative active core-shell material described herein can also effectively avoid situations such as silicon during negative pole as occurring because of Volumetric expansion negative pole appearance " dropping off ", " cracking ", make obtained battery while higher capacity is maintained, also with good cycle performance.
Brief description of the drawings
Fig. 1 be the embodiment of the present application 1 in negative active core-shell material A1 field emission scanning electron microscope figure.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that embodiment described herein is merely to illustrate and explain the present invention, it is not intended to limit the invention.
The present invention provides a kind of lithium ion battery anode active material, and the negative active core-shell material is core shell structure, and the core includes Li-Si alloy particle, and the shell is carbon-coating；Preferably, the shell is pyrolytic carbon layer.
According to lithium ion battery anode active material proposed by the present invention, it is preferable that on the basis of the weight of the Li-Si alloy particle, the content of lithium is 10-45%；The Li-Si alloy particle surface is coated to the active material of the core shell structure of carbon-coating is used for negative pole, due in Li-Si alloy particle, silicon materials have been " embedded " part lithium in advance, effectively it can prevent in battery charge and discharge process, silicon materials are by the situation of excessive " insertion " lithium, effectively alleviate the Volumetric expansion that silicon is used to occur during negative pole, simultaneously, the lithium being " embedded " in advance is during the later stage deviates from, hole can be left, to accommodate embedding lithium next time, further alleviate volumetric expansion effectiveness, so that the capacity and cycle performance of battery obtain very big lifting.
According to lithium ion battery anode active material proposed by the present invention, it is preferable that the average grain diameter of the Li-Si alloy particle is 0.2 ~ 5 μm；It is further preferred that the average grain diameter of the Li-Si alloy particle is 0.5 ~ 2 μm；Inventors herein have recognized that, the size of Li-Si alloy particle is controlled, can be in the influence that effectively reduction negative material is produced because silicon occurs volumetric expansion, while obtained negative active core-shell material also has good processing characteristics.
According to lithium ion battery anode active material proposed by the present invention, it is preferable that the porosity of the carbon-coating is less than 5%；The present inventor has found that the carbon shell for being less than 5% using porosity can be good at coordinating the charge-discharge performance of nuclear material Li-Si alloy so that negative material has the cycle performance of higher capacity and Geng Gao in an experiment.
According to lithium ion battery anode active material proposed by the present invention, the thickness of the carbon-coating is 5-10 μm；The presence of carbon shell, the discharge and recharge of nuclear material Li-Si alloy particle can not only be coordinated, make it have more preferable charge-discharge performance and cycle performance, simultaneously, the presence of the carbon shell can also reduce electrolyte and be contacted with the direct of Li-Si alloy particle, not only inhibit SEI films being concatenated to form on silicon materials surface, moreover it is possible to maintain the stabilization of inner nuclear material Li-Si alloy particle, the battery prepared also has good cycle performance while charge/discharge capacity is kept；And the thickness of carbon shell is defined to 5-10 μm, the negative active core-shell material of obtained core shell structure has optimal equalization performance.
According to lithium ion battery anode active material proposed by the present invention, the mass ratio of the Li-Si alloy particle and carbon-coating is 1：1~1：5；The mass ratio of Li-Si alloy particle and carbon-coating is controlled in above range value, carbon-coating can be made to form uniform and stable clad in Li-Si alloy particle surface.
According to lithium ion battery anode active material proposed by the present invention, it is characterised in that the carbon-coating also contains additive, the additive is the one or more in carbon black, CNT, carbon fiber, graphene, graphite microparticles；The presence of additive can improve the uniform and stable property of clad carbon-coating, while the electric conductivity of whole negative material can also be improved.
According to lithium ion battery anode active material proposed by the present invention, on the basis of the gross mass of the carbon-coating, the content of the additive is 1-20%.
The invention also provides a kind of preparation method of lithium ion battery anode active material, including：
(1) carbon source presoma, Li-Si alloy particle powder are mixed and disperseed with organic solvent, obtain slurries；
(2) removal organic solvent is dried in the slurries in step (1), obtains the presoma that carbon source presoma coats Li-Si alloy alloying pellet.
(3) presoma in step (2) is placed under inert atmosphere and be sintered, obtain the lithium ion battery anode active material that core is Li-Si alloy particle, shell is carbon-coating.
Preferably, in the step (1), the mass ratio of the carbon source presoma and Li-Si alloy particle powder is 5:1~20:1.The mass ratio of carbon source presoma and Li-Si alloy particle is controlled, and then can control to be coated on the carbon shell thickness of Li-Si alloy particle surface.
In above-mentioned steps (1), one or more of the carbon source presoma in glucose, polyethylene, polypropylene, polybutene, polyacrylonitrile, polyvinyl chloride, pitch, phenolic resin, sulphurated siliastic, paraffin, inclined tetrafluoroethene；The organic solvent is selected from the one or more in hexane, thiacyclohexane, heptane, octane, decane, ethylene carbonate, dimethyl ether, diethyl ether, phenylate, toluene, dimethylbenzene, tetrahydrofuran, oxinane, dimethyl sulfoxide, dimethylformamide, 1-METHYLPYRROLIDONE；The process for dispersing can be dispersed with stirring, it is preferred to use ultrasonic disperse；It is specifically as follows and carbon source presoma is first dissolved in organic solvent, then adds Li-Si alloy particle, dispersed with stirring or ultrasonic disperse, obtain dispersed slurries.
Drying means in above-mentioned steps (2) for example can remove organic solvent using the conventional method for removing organic solvent in this area using sol-gal process, spray drying process, fluid-bed drying or freeze-drying.
Sintering temperature in above-mentioned steps (3) is 400 ~ 1000 DEG C, and sintering time is 6 ~ 12h, is specially the product that will be obtained in step (2) in being incubated 6 ~ 12 hours in 400 ~ 1000 DEG C under inert gas shielding, furnace cooling；Wherein inert gas is protective gas commonly used in the art, such as nitrogen, argon gas.
According to the preparation method of lithium ion battery anode active material proposed by the present invention, preferably, also include adding additive, one or more of the additive in carbon black, CNT, carbon fiber, graphene, graphite microparticles in the step (1).
Present invention further proposes a kind of negative electrode of lithium ion battery, the negative pole includes the lithium ion battery anode active material that the application is proposed.
The invention also provides a kind of lithium ion battery, the battery includes above-mentioned negative pole.
In the present invention, the positive pole of battery, barrier film and nonaqueous electrolyte liquid are had no particular limits, can be with various types of positive poles, barrier film and nonaqueous electrolytic solution commonly used in the art, as long as the negative pole that the battery is used contains the negative active core-shell material of core shell structure provided by the present invention.The preparation method of the negative pole can use various methods commonly used in the art, for example negative active core-shell material proposed by the present invention, negative pole can be bonded and mixed with negative pole organic solvent, be coated on negative electrode collector, negative electrode material layer is formed on negative current collector surface, dry, obtain the negative pole.Preferably, in the negative electrode material layer of the battery, the content for the negative active core-shell material that the present invention is provided is 80-100wt%；The species and content of the negative pole bonding agent can be the conventional selection of this area.For example, the negative pole bonding agent can be selected from carboxymethyl cellulose（CMC）, Kynoar（PVDF）, polytetrafluoroethylene (PTFE)（PTFE）, polyvinyl alcohol（PVA）, polyacrylic acid（PAA）, chitosan, sodium alginate, polyimides, butadiene-styrene rubber（SBR）At least one of with the various modifications such as TPO emulsion or non-modified bonding agent.Preferably, on the basis of the gross weight of negative active core-shell material, the content of the negative pole bonding agent is 0.01%-10%, preferably 0.02%-8%；The negative electrode material layer can optionally contain cathode conductive agent, and the cathode conductive agent is selected from least one of carbon black, nickel powder and copper powder, and to increase negative conductive, the consumption of cathode conductive agent is known to the skilled person.
The positive pole is known to those skilled in the art.The positive pole includes plus plate current-collecting body and coating and/or the positive electrode being filled on plus plate current-collecting body, and the positive electrode includes positive active material, positive conductive agent and positive electrode binder.
The preparation method of the positive pole is various methods commonly used in the art, for example, positive active material, positive conductive agent and positive electrode binder can be mixed with positive pole organic solvent, be coated on positive electrode collector, be dried to obtain the positive pole.
According to the present invention, the various positive active materials that the positive active material can be known in the art for example can be LiCoO2、LiVPO4、LiCoAlO2、LiMnCoO2、LiCoxNiyMnzO2（x+y+z=1）、LiMn2O4、LiNiO2And LiFexM1-xPO4（M is Co, Ni, Mn, 0.8≤x≤1）In one or more, wherein the consumption of the positive active material be this area conventional amount used.
The present invention is not particularly limited for the positive conductive agent in positive pole, can be the conventional positive conductive agent in this area, for example can be selected from least one of carbon black, graphite, acetylene black, carbon fiber, CNT, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder, the consumption of positive conductive agent can be the conventional amount used of ability.Generally on the basis of the gross weight of positive active material, the content of positive conductive agent can be 0.5%-15%, preferably 1%-10%.
According to the present invention, the positive electrode binder can be various positive electrode binders commonly used in the art, for example can selected from polyvinylidene fluoride, polytetrafluoroethylene (PTFE),（It is fluorine-containing）Polyacrylate,（It is fluorine-containing）Polyurethane,（It is fluorine-containing）Epoxy resin, polyacrylic acid（PAA）, chitosan, sodium alginate, polyimides, butadiene-styrene rubber, poly- methylcellulose, poly- sodium carboxymethylcellulose pyce, hydroxypropyl methyl cellulose, POLYPROPYLENE GLYCOL and butadiene-styrene rubber（SBR）In one or more.Further, on the basis of the gross weight of positive active material, the content of the positive electrode binder is 0.01%-10%, preferably 0.02%-7%.
According to the present invention, the positive pole organic solvent and negative pole organic solvent can be conventional use of various organic solvents in this area, for example, can be the one or more in 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO), tetrahydrofuran and water and alcohol series solvent.
The both positive and negative polarity collector that the plus plate current-collecting body negative current collector is known to the skilled person, for example, can be one kind in aluminium foil, copper foil, Punching steel strip.
The barrier film is located between positive pole and negative pole.The barrier film is not particularly limited in the present invention, can be conventional use of various barrier films, such as polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper in lithium ion battery.
The nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and there is no particular limitation as to it, the nonaqueous electrolytic solution that this area can be used conventional.Such as electrolyte lithium salt can be selected from lithium hexafluoro phosphate（LiPF6）, lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, at least one of chlorine lithium aluminate and fluorohydrocarbon base Sulfonic Lithium.Nonaqueous solvents can select chain acid esters and ring-type acid esters mixed solution, and wherein chain acid esters can be selected from dimethyl carbonate（DMC）, diethyl carbonate（DEC）, methyl ethyl carbonate（EMC）, methyl propyl carbonate（MPC）, dipropyl carbonate（DPC）And at least one of other fluorine-containing, sulfur-bearings or the chain organosilane ester containing unsaturated bond, ring-type acid esters can be selected from ethylene carbonate（EC）, propene carbonate（PC）, vinylene carbonate（VC）, gamma-butyrolacton（γ-BL）, sultone and at least one of other fluorine-containing, sulfur-bearings or the ring-type organosilane ester containing unsaturated bond.Generally, in nonaqueous electrolytic solution, the concentration of lithium salts is 0.1-2.0mol/L.
According to the present invention, other constructions and preparation method of the battery are known to the skilled person, and therefore not to repeat here.
Because above-mentioned battery employs the negative active core-shell material for the core shell structure that the present invention is provided, it can preferably alleviate the volumetric expansion problem of silicium cathode material, so that the battery of gained has preferable cycle performance while high power capacity is ensured.
Below by way of specific embodiment, the present invention is described in detail.
Wherein, in the application, the porosity of carbon shell is measured by BET, mercury injection method；The thickness of carbon shell is measured by TG-DSC, TEM.
Embodiment
1
(1) 10g polyacrylonitrile is taken to be dissolved in 100ml dimethylformamide, form 100g/L solution, the Li-Si alloy particle powder that 2g average grain diameters are 1000nm is taken (in Li-Si alloy particle powder, 44%) the weight ratio of lithium is, under electromagnetic agitation, Li-Si alloy particle powder is put into above-mentioned solution, ultrasonic disperse after stirring obtains slurries；
(2) slurries in step (1) are placed under argon atmosphere and be spray-dried under 80 DEG C of environment, obtain the presoma that carbon source presoma coats Li-Si alloy alloying pellet；
(3) presoma in step (2) is placed in the dry crucible of graphite, in being incubated 6h at 800 DEG C under argon atmosphere, the lithium ion battery anode active material A1 that core is Li-Si alloy particle, shell is carbon-coating is obtained after cooling；Negative active core-shell material A1 Flied emission electron-microscope scanning figure is as shown in Figure 1；
(4) negative active core-shell material that will be prepared by quality proportioning in step (3)：Acetylene black：CMC：SBR=100：2：1.5：Tabletting after 2.5 ratio is well mixed, 120 DEG C of vacuum drying 24h obtain testing pole piece；Using metal lithium sheet as to electrode, celgard2400 polypropylene porous films are barrier film, 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC)（Weight ratio is=1：1）Mixed solution assembled in the glove box full of argon gas for electrolyte, so as to prepare battery S1.
Embodiment
2
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, step (1) substitutes polyacrylonitrile by adding 10g polyvinyl alcohol, prepares negative active core-shell material A2 and battery S2.
Embodiment
3
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 20g, the average grain diameter of the Li-Si alloy particle powder of addition is 500nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A3 and battery S3.
Embodiment
4
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 10g, the average grain diameter of the Li-Si alloy particle powder of addition is 800nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A4 and battery S4.
Embodiment
5
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 20g, the average grain diameter of the Li-Si alloy particle powder of addition is 1000nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A5 and battery S5.
Embodiment
6
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 10g, the average grain diameter of the Li-Si alloy particle powder of addition is 1500nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A6 and battery S6.
Embodiment
7
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 20g, the average grain diameter of the Li-Si alloy particle powder of addition is 2000nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A7 and battery S7.
Embodiment
8
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, also include adding additive in step (1), additive is 0.5g graphene and 0.5g carbon ink, prepares negative active core-shell material A8 and battery S8.
Embodiment
9
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, also include adding additive in step (1), additive is 0.5g CNT and 0.5g graphite microparticles, prepares negative active core-shell material A9 and battery S9.
Comparative example
1
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, Li-Si alloy powder is replaced using Si powder in step (1), negative active core-shell material DA1 and battery DS1 is prepared.
Comparative example
2
Battery is prepared using method same as Example 1, unlike, the Li-Si alloy powder particle for being 1000nm with average grain diameter in step (4) directly replaces the negative active core-shell material prepared in step (3), the Li-Si alloy powder particle is directly designated as DA2, and the battery prepared is designated as DS2.
Performance test
1st, charge-discharge performance is tested
Battery S1-S9, DS1-DS2 are subjected to electrochemical property test under room temperature environment, charging and discharging currents are 0.2C, and blanking voltage is 0.005 ~ 0.8V, and test result is shown in Table 1.
2nd, cycle performance is tested
Battery S1-S9 and DS1-DS2 are subjected to charge-discharge performance test, test condition is：First with 0.5C constant-current discharges to 0.005V, then with 0.2C constant-current discharges to 0.005V, shelve 5 minutes；0.8V is charged to 0.5C, is shelved 5 minutes；Circulation 50 times, after circulation terminates, by the 50th capacity divided by circulation volume produces capability retention first, test result is shown in Table 1.
Table 1
。
Wherein, efficiency refers to efficiency for charge-discharge, is the percentage of de- lithium capacity and embedding lithium capacity.Capability retention refers to take off lithium specific discharge capacity after circulating 50 times with taking off the percentage of lithium specific discharge capacity first.
As shown in Table 1, the negative active core-shell material of the core shell structure provided using the application is used for negative pole, and lithium capacity is taken off first and is far longer than embedding lithium capacity first, and this is due to during de- lithium, the lithium being " embedded " in advance is also deviate from the lump, therefore de- lithium amount is far longer than lithium-inserting amount first first；It can thus be seen that the negative active core-shell material that the application is provided, effectively can prevent silicon materials from occurring serious Volumetric expansion because being excessively embedded lithium in battery charge and discharge process；The battery S1-S9 that the negative active core-shell material of the core shell structure provided simultaneously using the present invention is made takes off the minimum 363.5mAh/g of lithium specific capacity after circulating 50 times, it is far longer than 216.4 mAh/g in 132.7 mAh/g and the DS2 in DS1, capability retention reaches as high as 83.5% after circulating 50 times, it is therefore seen that, the battery that negative active core-shell material provided by the present invention is prepared, with good cycle performance.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the range of the technology design of the present invention; a variety of simple variants can be carried out to technical scheme, these simple variants belong to protection scope of the present invention.
Claims (17)
1. a kind of lithium ion battery anode active material, it is characterised in that the negative active core-shell material is core shell structure, the core includes Li-Si alloy particle, and the shell is carbon-coating.
2. lithium ion battery anode active material according to claim 1, it is characterised in that on the basis of the weight of the Li-Si alloy particle, the content of lithium is 10-45%.
3. lithium ion battery anode active material according to claim 1, it is characterised in that the average grain diameter of the Li-Si alloy particle is 0.2 ~ 5 μm.
4. lithium ion battery anode active material according to claim 3, it is characterised in that the average grain diameter of the Li-Si alloy particle is 0.5 ~ 2 μm.
5. lithium ion battery anode active material according to claim 1, it is characterised in that the porosity of the carbon-coating is less than 5%.
6. lithium ion battery anode active material according to claim 1, it is characterised in that the thickness of the carbon-coating is 3-10 μm.
7. lithium ion battery anode active material according to claim 1, it is characterised in that the mass ratio of the Li-Si alloy particle and carbon-coating is 1：1~1：5.
8. lithium ion battery anode active material according to claim 1, it is characterised in that the carbon-coating is pyrolytic carbon layer.
9. lithium ion battery anode active material according to claim 8, it is characterised in that the carbon-coating also contains additive, the additive is the one or more in carbon black, CNT, carbon fiber, graphene, graphite microparticles.
10. lithium ion battery anode active material according to claim 8, it is characterised in that on the basis of the gross mass of the carbon-coating, the content of the additive is 1-20%.
11. a kind of preparation method of lithium ion battery anode active material, it is characterised in that including：
(1) carbon source presoma, Li-Si alloy particle powder are mixed and disperseed with organic solvent, obtain slurries；
(2) removal organic solvent is dried in the slurries in step (1), obtains the presoma that carbon source presoma coats Li-Si alloy alloying pellet；
(3) presoma in step (2) is placed under inert atmosphere and be sintered, obtain the lithium ion battery anode active material that core is Li-Si alloy particle, shell is carbon-coating.
12. the preparation method of lithium ion battery anode active material according to claim 11, it is characterised in that the mass ratio of carbon source presoma and Li-Si alloy particle powder is 5 in the step (1):1~20:1.
13. the preparation method of lithium ion battery anode active material according to claim 11, characterized in that, one or more of the carbon source presoma in glucose, polyethylene, polypropylene, polybutene, polyacrylonitrile, polyvinyl chloride, pitch, phenolic resin, sulphurated siliastic, paraffin, inclined tetrafluoroethene；The organic solvent is selected from the one or more in hexane, thiacyclohexane, heptane, octane, decane, ethylene carbonate, dimethyl ether, diethyl ether, phenylate, toluene, dimethylbenzene, tetrahydrofuran, oxinane, dimethyl sulfoxide, dimethylformamide, 1-METHYLPYRROLIDONE.
14. the preparation method of lithium ion battery anode active material according to claim 11, it is characterized in that, also include adding additive, one or more of the additive in carbon black, CNT, carbon fiber, graphene, graphite microparticles in the step (1).
15. the preparation method of lithium ion battery anode active material according to claim 14, it is characterised in that sintering temperature is 400 ~ 1000 DEG C in the step (3), sintering time is 6 ~ 12h.
16. a kind of negative electrode of lithium ion battery, it is characterised in that the negative pole includes the lithium ion battery anode active material described in claim 1-9 any one.
17. a kind of lithium ion battery, it is characterised in that the battery includes the negative pole described in claim 16.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108574091A (en) * | 2018-04-12 | 2018-09-25 | 合肥国轩高科动力能源有限公司 | A kind of new type lithium ion battery vanadium base hydride negative material and preparation method thereof |
| CN109461911A (en) * | 2018-10-22 | 2019-03-12 | 江西省科学院科技战略研究所(江西省科学院科技信息中心) | A kind of cladded type Li-Si alloy and its preparation method and application |
| CN109585838A (en) * | 2018-12-27 | 2019-04-05 | 蜂巢能源科技有限公司 | Silicon-carbon cathode material and preparation method thereof, power battery and electric vehicle |
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| US11316147B2 (en) * | 2016-02-15 | 2022-04-26 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and method for producing negative electrode active material |
| WO2022194089A1 (en) * | 2021-03-19 | 2022-09-22 | 比亚迪股份有限公司 | Negative electrode material and preparation method therefor, and all-solid-state lithium battery |
| CN115241448A (en) * | 2022-09-22 | 2022-10-25 | 北京阿特精思智能科技有限公司 | Honeycomb-structured carbon-silicon-lithium-carbon-based nano composite material and preparation method thereof |
Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07326342A (en) * | 1994-05-30 | 1995-12-12 | Mitsubishi Cable Ind Ltd | Negative electrode for lithium secondary battery, and lithium secondary battery using the same |
| US6383686B1 (en) * | 1999-01-26 | 2002-05-07 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, lithium secondary battery using said anode material, and method for charging of said secondary battery |
| CN1717822A (en) * | 2002-11-26 | 2006-01-04 | 昭和电工株式会社 | Electrode material comprising silicon and/or tin particles and production method and use thereof |
| CN1738075A (en) * | 2004-08-17 | 2006-02-22 | 比亚迪股份有限公司 | Lithium alloy composite material and its preparing method, minus pole material, negative pole structure and lithium secondary cells |
| CN1795573A (en) * | 2003-06-25 | 2006-06-28 | 株式会社Lg化学 | Anode material for lithium secondary cell with high capacity |
| CN1909268A (en) * | 2006-07-10 | 2007-02-07 | 深圳市贝特瑞电子材料有限公司 | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method |
| JP2007335086A (en) * | 2006-06-12 | 2007-12-27 | Matsushita Electric Ind Co Ltd | Manufacturing method of electrode for lithium battery |
| CN102332571A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece |
| US8241793B2 (en) * | 2009-01-02 | 2012-08-14 | Nanotek Instruments, Inc. | Secondary lithium ion battery containing a prelithiated anode |
| CN102709565A (en) * | 2012-05-30 | 2012-10-03 | 力芯（青岛）新能源材料有限公司 | Preparation method of lithium ion battery porous silicon carbon composite negative material |
| CN102754250A (en) * | 2010-02-19 | 2012-10-24 | 松下电器产业株式会社 | Coin-shaped lithium secondary battery |
| CN102832378A (en) * | 2012-08-28 | 2012-12-19 | 浙江瓦力新能源科技有限公司 | Carbon anode material for lithium ion battery and preparation method for carbon anode material |
| CN102867983A (en) * | 2011-07-04 | 2013-01-09 | 中国人民解放军63971部队 | Nonaqueous secondary lithium battery |
| CN103219504A (en) * | 2013-03-28 | 2013-07-24 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof |
| CN103280571A (en) * | 2013-05-27 | 2013-09-04 | 华南师范大学 | Positive pole material of lithium ion battery and preparation method of positive pole material |
| CN104091920A (en) * | 2014-07-17 | 2014-10-08 | 黄冈师范学院 | Carbon-coated nano-scale lithium-aluminum alloy negative electrode material and preparation method thereof |
| CN104124431A (en) * | 2014-08-12 | 2014-10-29 | 湖南元素密码石墨烯研究院（有限合伙） | Graphite negative electrode material for lithium ion battery and preparation method of graphite negative electrode material |
| CN104766965A (en) * | 2014-01-03 | 2015-07-08 | 中国科学院物理研究所 | Nanometer lithium silicon alloy material, and preparation method and use thereof |
| CN105098250A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力***（湖州）有限公司 | Lithium ion battery with lithium-free positive plate |
| CN105098138A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力***（湖州）有限公司 | Negative plate used for lithium ion battery and preparation method thereof |
| CN105118971A (en) * | 2015-07-06 | 2015-12-02 | 新乡远东电子科技有限公司 | Lithium ion battery negative electrode material and preparation method |
| CN105359304A (en) * | 2013-03-13 | 2016-02-24 | 新强能电池公司 | Silicon particles for battery electrodes |
-
2016
- 2016-03-31 CN CN201610204053.4A patent/CN107293701A/en active Pending
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07326342A (en) * | 1994-05-30 | 1995-12-12 | Mitsubishi Cable Ind Ltd | Negative electrode for lithium secondary battery, and lithium secondary battery using the same |
| US6383686B1 (en) * | 1999-01-26 | 2002-05-07 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, lithium secondary battery using said anode material, and method for charging of said secondary battery |
| CN1717822A (en) * | 2002-11-26 | 2006-01-04 | 昭和电工株式会社 | Electrode material comprising silicon and/or tin particles and production method and use thereof |
| CN1795573A (en) * | 2003-06-25 | 2006-06-28 | 株式会社Lg化学 | Anode material for lithium secondary cell with high capacity |
| CN1738075A (en) * | 2004-08-17 | 2006-02-22 | 比亚迪股份有限公司 | Lithium alloy composite material and its preparing method, minus pole material, negative pole structure and lithium secondary cells |
| JP2007335086A (en) * | 2006-06-12 | 2007-12-27 | Matsushita Electric Ind Co Ltd | Manufacturing method of electrode for lithium battery |
| CN1909268A (en) * | 2006-07-10 | 2007-02-07 | 深圳市贝特瑞电子材料有限公司 | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method |
| US8241793B2 (en) * | 2009-01-02 | 2012-08-14 | Nanotek Instruments, Inc. | Secondary lithium ion battery containing a prelithiated anode |
| CN102754250A (en) * | 2010-02-19 | 2012-10-24 | 松下电器产业株式会社 | Coin-shaped lithium secondary battery |
| CN102867983A (en) * | 2011-07-04 | 2013-01-09 | 中国人民解放军63971部队 | Nonaqueous secondary lithium battery |
| CN102332571A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece |
| CN102709565A (en) * | 2012-05-30 | 2012-10-03 | 力芯（青岛）新能源材料有限公司 | Preparation method of lithium ion battery porous silicon carbon composite negative material |
| CN102832378A (en) * | 2012-08-28 | 2012-12-19 | 浙江瓦力新能源科技有限公司 | Carbon anode material for lithium ion battery and preparation method for carbon anode material |
| CN105359304A (en) * | 2013-03-13 | 2016-02-24 | 新强能电池公司 | Silicon particles for battery electrodes |
| CN103219504A (en) * | 2013-03-28 | 2013-07-24 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof |
| CN103280571A (en) * | 2013-05-27 | 2013-09-04 | 华南师范大学 | Positive pole material of lithium ion battery and preparation method of positive pole material |
| CN104766965A (en) * | 2014-01-03 | 2015-07-08 | 中国科学院物理研究所 | Nanometer lithium silicon alloy material, and preparation method and use thereof |
| CN105098250A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力***（湖州）有限公司 | Lithium ion battery with lithium-free positive plate |
| CN105098138A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力***（湖州）有限公司 | Negative plate used for lithium ion battery and preparation method thereof |
| CN104091920A (en) * | 2014-07-17 | 2014-10-08 | 黄冈师范学院 | Carbon-coated nano-scale lithium-aluminum alloy negative electrode material and preparation method thereof |
| CN104124431A (en) * | 2014-08-12 | 2014-10-29 | 湖南元素密码石墨烯研究院（有限合伙） | Graphite negative electrode material for lithium ion battery and preparation method of graphite negative electrode material |
| CN105118971A (en) * | 2015-07-06 | 2015-12-02 | 新乡远东电子科技有限公司 | Lithium ion battery negative electrode material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| SHINICHIROH IWAMURA等: "Li-Rich Li-Si Alloy As A Lithium-Containing Negative Electrode Material Towards High Energy Lithium-Ion Batteries", 《SCIENTIFIC REPORTS》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11316147B2 (en) * | 2016-02-15 | 2022-04-26 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and method for producing negative electrode active material |
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| CN114388790A (en) * | 2020-10-21 | 2022-04-22 | 比亚迪股份有限公司 | Battery prelithiation slurry, battery negative plate and lithium ion battery |
| CN114388790B (en) * | 2020-10-21 | 2023-11-14 | 比亚迪股份有限公司 | Pre-lithiation slurry for battery, negative plate for battery and lithium ion battery |
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| CN115241448A (en) * | 2022-09-22 | 2022-10-25 | 北京阿特精思智能科技有限公司 | Honeycomb-structured carbon-silicon-lithium-carbon-based nano composite material and preparation method thereof |
| CN115241448B (en) * | 2022-09-22 | 2022-12-09 | 北京阿特精思智能科技有限公司 | Honeycomb-structured carbon-silicon-lithium-carbon-based nano composite material and preparation method thereof |
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