CN102122708A - Negative pole material for lithium-ion secondary battery, negative pole containing negative pole material, preparation method of negative pole and battery containing negative pole - Google Patents

Negative pole material for lithium-ion secondary battery, negative pole containing negative pole material, preparation method of negative pole and battery containing negative pole Download PDF

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CN102122708A
CN102122708A CN2010100340081A CN201010034008A CN102122708A CN 102122708 A CN102122708 A CN 102122708A CN 2010100340081 A CN2010100340081 A CN 2010100340081A CN 201010034008 A CN201010034008 A CN 201010034008A CN 102122708 A CN102122708 A CN 102122708A
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negative pole
negative
preparation
carbon
battery
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钟开富
李泓
黄学杰
陈立泉
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Institute of Physics of CAS
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Abstract

The invention relates to a negative pole material for a lithium-ion secondary battery, and the negative pole material comprises composite particles in core-shell structures, conductive additives and an amide type high-temperature-resistant binder, wherein each composite particle in the core-shell structure comprises an inner core and an outer shell layer, each inner core contains at least one of elemental silicon, a silicon oxide and a silicon alloy, and each outer shell layer is coated by one or more of inorganic materials, namely C, Cu, Ni, Fe, Cr, Al2O3, TiO2, LiPO3, Li2Si2O5, Li2SiO3, Li4SiO4, Li8SiO6 and SiO2; and the amide type high-temperature-resistant binder is one or more of polyamide, imide and amide-imide. The invention further relates to a negative pole containing the negative pole material and a preparation method thereof. The invention further relates to a battery containing the negative pole. The battery has the advantages of higher charge-discharge capacity, better cycle property and high safety, and is suitable for various mobile electronic devices or devices requiring mobile energy sources for driving.

Description

Be used for lithium rechargeable battery negative material, contain the negative pole and preparation method thereof of this negative material and the battery that contains this negative pole
Technical field
The present invention relates to a kind of negative material that is used for lithium rechargeable battery, contain the negative pole and preparation method thereof of this negative material and the battery that contains this negative pole.
Background technology
The fast development of portable devicesization and various electronic components increases day by day to the demand of high-energy density secondary battery, and wherein, lithium rechargeable battery is with its specific energy height, and is light, and characteristics such as operating voltage height become chemical power source development in future direction.At present, the negative pole of lithium rechargeable battery mainly uses material with carbon element, for example petroleum coke, carbon fiber, RESEARCH OF PYROCARBON, native graphite, Delanium etc., apply for a patent in March, 1989 by Japanese Sony Corporation at first, input in 1992 commercialization (referring to Bu Lunuo, electrochemistry meeting will, 139 volumes, 2776 pages, 1992).Yet near the theoretical capacity (372mAh/g) of graphite, therefore, it is very difficult that desire further improves its theoretical capacity by the improvement material with carbon element to the negative material that the employing material with carbon element is made.
Can cause concern very early as the negative material of lithium battery with the silicon of lithium generation alloying reaction, its theoretical capacity is 4400mAh/g, much larger than the theoretical capacity of graphite.But discover that the battery of siliceous negative material is followed huge bulk effect in charge and discharge process, cause the silicon grain efflorescence, come off, lose gradually and electrically contact, thereby make the non-constant of electrode cyclicity.In addition, though as document H.Li, X.J.Huang, L.Q.Chen, Z.G.Wu, Y.Liang, Electr Chem.and Solid-StateLett., 2, reported among the 547-549 (1999), the Si particle is reduced to nanoscale, and itself and conductive additive are evenly disperseed, can effectively improve the cyclicity of electrode, but first all efficient (65%) and capability retention are relatively poor, main cause is that nano material has bigger surface energy, easily reunites in charge and discharge process, and nano material has bigger specific surface simultaneously, cause more side reaction, comprise the passivating film (SEI film) of superficial growth electronic isolation, the active particle conductive network is variation gradually, finally causes low coulombic efficiency and capability retention.Therefore prepare the negative material of nanoscale, need reduce its specific surface, improve tap density its structural design.
Disclose among Chinese patent application 200410030990.X and the Chinese patent application 200510082822.X by chemical vapor deposition (CVD) carbon directly has been coated on the material that silicon face forms nucleocapsid structure, the cyclicity of this material and first all coulomb efficient increase, but in charge and discharge process, be coated on inner silicon grain because change in volume is bigger, make nucleocapsid structure can't keep stable structure, finally efflorescence gradually, electrically contact variation between the silicon grain, so the silicon grain of considerable part is because polarization and do not demonstrate due electro-chemical activity; In addition, owing to still can contact with electrolyte after the efflorescence, the surface unsettled SEI film that regrows causes the part active particle to lose electro-chemical activity gradually.
Recently, also there is method by physical deposition on conductive substrates, to deposit one deck silicon thin film and prepares membrane electrode.The cyclicity of prepared silicon thin film electrode is relevant with the thickness of film, and when the thickness of film during less than 4 μ m, cyclicity is very good, and efficiency for charge-discharge height (93-95%).But,, make that active material is less on the unit are collector, so the energy density of battery is not high because membrane electrode has the restriction of thickness.
In addition, although by material modification,, can go up the chemical property that improves electrode largely such as methods such as the Si that chooses small scale, carbon coating, Si alloys.But electrode still exists certain bulk effect in charge and discharge process.
High performance binding agent plays important effect for the material capacity conservation rate.Many research reports adopt high resiliency, or the binding agent of high-tensile can better improve the cyclical stability of Si negative pole than Kynoar on the traditional sense (PVDF).
Comprehensive above consideration, the present invention comprehensively improves high power capacity negative material Si, the battery that the negative material that contains high-performance adhesive, the negative pole that contains this negative material and preparation method thereof is provided and has contained this negative pole.
Summary of the invention
The present invention overcomes that existing negative material cycle performance is poor, reversible capacity is low, take off lithium current potential height and the low defective of coulombic efficiency, a kind of negative material that can make serondary lithium battery have higher charge/discharge capacity, cycle characteristics and fail safe preferably is provided, contain negative pole of this negative material and preparation method thereof, and the battery that contains this negative pole.
The objective of the invention is to be achieved through the following technical solutions:
On the one hand, the invention provides a kind of negative material that is used for lithium rechargeable battery, this negative material comprises compound particle, conductive additive and the amide-type high temperature resistant binder with nucleocapsid structure.
Preferably, the compound particle of described nucleocapsid structure comprises: the kernel and the outer shell that contains inorganic clad material that contain silica-based active material.
Preferably, described silica-based active material is one or more in silicon, Si oxide, the silicon alloy;
Preferably, described silica-based active material can also be mixed with one or more in material with carbon element, tin simple substance, tin-oxide, ashbury metal, manganous oxide and the chromium oxide.
Preferably, described inorganic clad material is C, Cu, Fe, Ni, Cr, Al 2O 3, TiO 2, Li 2Si 2O 5, Li 2SiO 3, Li 4SiO 4, Li 8SiO 6, SiO 2And Li 3PO 4In one or more.
Preferably, the particle diameter of described kernel is 10 nanometers-4 micron, is preferably 50 nanometers-4 micron, more preferably 500 nanometers-2 micron.
Preferably, described outer shell thickness is 1 nanometer-500 nanometer, is preferably 50 nanometers-100 nanometer, more preferably 50 nanometers-80 nanometer.
Preferably, the particle diameter of the compound particle of described nucleocapsid structure is 100 nanometers～100 micron, is preferably 1 micron～20 microns.
Preferably, described conductive additive is a graphite powder, conductive black, acetylene black, carbon nano-tube, for example Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, carbon fiber, one or more in metal powder and the metallic fiber;
Preferably, the particle diameter of described graphite powder, conductive black, acetylene black or metal powder is 1 nanometer-20 micron;
More preferably, the length of described carbon nano-tube, carbon fiber or metallic fiber is 10 nanometers-20 micron, and diameter is 10 nanometers-500 nanometers.
Preferably, described amide-type high temperature resistant binder is one or more in polyamidoimide, polyamide, the polyimides;
Be preferably in aromatic polyamide acid imide, aromatic polyamide, the aromatic polyimide one or more.
Preferably, the compound particle of described nucleocapsid structure accounts for 3～98wt% of described negative material total weight, is preferably 20～95wt%; Described conductive additive accounts for 1～35wt% of described negative material total weight, is preferably 5-10wt%; Described amide-type high temperature resistant binder accounts for the 1-30wt% of described negative material total weight, is preferably 5-15wt%, more preferably 10wt%.
On the other hand, the invention provides a kind of negative pole that is used for lithium rechargeable battery, described negative pole comprises above-mentioned negative material and collector; Preferably, described collector is the carrier of paper tinsel, net, porous body, foams or the corpus fibrosum material of various conductions, for example Copper Foil, nickel screen, nickel foam and carbon felt.
Again on the one hand, the invention provides a kind of preparation method of above-mentioned negative pole, this preparation method comprises: with silica-based active material, conductive additive, adhesive coated on collector, in vacuum or inert atmosphere, at 80-450 ℃, be preferably 120 ℃-350 ℃, more preferably heat-treat for 120 ℃-300 ℃, heat treatment time is 10 minutes-10 hours.
Another aspect the invention provides a kind of lithium rechargeable battery, and this secondary cell comprises above-mentioned negative pole.
Technical scheme of the present invention has following beneficial effect compared with prior art at least:
1, compare with the negative material of existing battery, negative material of the present invention adopts nucleocapsid structure, and like this, the change in volume of the active material of kernel in charge and discharge process can be subjected to outer shell and suppress, thereby reduces bulk effect; In addition, owing to adopt nucleocapsid structure, the growth of surface passivated membrane is only relevant with outer shell active sites area size, can reduce the growth of passivating film.
2, compare with the negative material of existing battery, negative material of the present invention has adopted high-performance amide-type binding agent, it is the amide-type high temperature resistant binder, this high performance binding agent plays important effect for the material capacity conservation rate, and the present invention adopts the binding agent of high-tensile can better improve the cyclical stability of Si negative pole.
3, compare the chemical property excellence of negative material of the present invention, lithium storage content height with the negative material of existing battery.
4, compare with the method for existing preparation electrode, the present invention adopts high-temperature heat treatment method to prepare electrode, make incomplete amidated polyamidoimide amidatioon in the binding agent, strand further increases, also can take place crosslinked simultaneously between the strand segment, significantly improve quality of forming film, obtain high-intensity adhesive property, and and then guaranteed the long-time cyclical stability of negative pole.And the bonding agent of prior art employing at present such as Kynoar, carboxymethyl carbonic ester etc. are mainly applying below 120 ℃, and high temperature can decompose, and these bonding agents can't obtain high-intensity adhesive property.
Below will be described in more detail the present invention.
The objective of the invention is to, be provided for the negative material of lithium rechargeable battery.Another object of the present invention is to, the electrode that contains above-mentioned negative material is provided.A further object of the present invention is, provides silica-based active material, amide-type high temperature resistant binder, conductive additive are coated on the manufacture craft for preparing electrode on the collector.A further object of the present invention is, the battery that contains above-mentioned electrode is provided.
Negative material of the present invention comprises compound particle, conductive additive and the binding agent with nucleocapsid structure.
Above-mentioned compound particle has nucleocapsid structure, and particle diameter is 100 nanometers～100 micron.Described nucleocapsid structure comprises kernel and outer shell; Described kernel is chosen elementary silicon, Si oxide, at least a in the silicon alloy, also can select to add the commodity material with carbon element, tin simple substance, tin-oxide and ashbury metal, manganous oxide, in the chromium oxide one or more, particle diameter are preferably 50 nanometers-4 micron, and it is the particle of irregular, spheric granules or almost spherical; Described outer shell be one or more layers, equally distributed continuous film, or point, or grid depend on the variation of preparation condition.The surface coated inorganic material of described outer shell can be C, Cu, Fe, Cr, Ni, Al 2O 3, TiO 2,, Li 2Si 2O 5, Li 2SiO 3, Li 4SiO 4, Li 8SiO 6, SiO 2, Li 3PO 4, Li 2Among the O one or more, the thickness of coating layer are 1 nanometer-500 nanometer.
Wherein, the carbon-coating of coating is the good electron ion conductor, also can be used as the buffer medium of Si change in volume simultaneously.The Cu that coats, Fe, Ni, Cr layer be diffusion easily in Si, be beneficial to raising Si material electronics electricity and lead continuous Cu, Fe, Ni, the Cr layer has ductility preferably, can effectively alleviate the change in volume of Si, through Overheating Treatment, Cu, Fe, Ni, Cr and Si form the alloy of electronic conductor easily, and the interface contact is also better, even Si particle generation change in volume also can keep excellent contact, keep whole conductive network.Al 2O 3, TiO 2, Li 2Si 2O 5, Li 2SiO 3, Li 4SiO 4, Li 8SiO 6, SiO 2, Li 3PO 4The surface coated thickness of may command helps reducing the active sites that material surface exposes, and reduces the SEI film and generates, thereby improve coulombic efficiency.
Described conductive additive accounts for 1～35wt% of described negative material total weight, and this conductive additive comprises graphite powder, conductive black, acetylene black, carbon nano-tube (Single Walled Carbon Nanotube, multi-walled carbon nano-tubes), carbon fiber, metal powder and metallic fiber; The particle diameter of described graphite powder, conductive black, acetylene black and metal powder is 1 nanometer to 20 micron; The length of described carbon nano-tube, carbon fiber and metallic fiber is 10 nanometers to 20 micron, and diameter is that 10 nanometers are to 500 nanometers.
Described binding agent can be polyamidoimide, polyamide, at least a macromolecule in the polyimides, perhaps above-mentioned not complete a kind of in the macromolecule of polymerization.Consider chemical stability, mechanical property and adhesive property, binding agent is preferably the aromatic polyamide acid imide, aromatic polyamide, one or more of aromatic polyimide family macromolecule.The consumption of described binding agent preferably accounts for the 1-30% of described negative material total weight.When this consumption less than 1%, the hypodynamic situation that bonds can appear, when this consumption greater than 30%, can have influence on the capacity of material.
Above-mentioned macromolecule major part all has good thermal stability, and chemical stability has higher tensile strength, and strong adhesiveness makes the high power capacity negative material have excellent cycle characteristics.Polar group on these macromolecules makes it have good adhesive force on the one hand, also is beneficial to the transmission of lithium ion on the other hand, and the molecular chain structure of itself makes it have tensile strength preferably.In addition, adopt 80 ℃-450 ℃ Temperature Treatment, for not fully the macromolecule of polymerization can advance one one crosslinked, strand can further increase, and can improve quality of forming film, helps the stable of electrode structure, thereby improves chemical property.
The compound particle (negative active core-shell material) that the present invention has nucleocapsid structure can adopt (I) spray drying process; (II) chemical deposition coats method; (III) Mechanical Method; (IV) hydro thermal method; (V) method such as chemical vapour deposition technique prepares.
(I) use spray drying method for preparation the present invention to be used for the negative active core-shell material of secondary lithium battery, comprise following step:
(1) inner active material Si is carried out surface treatment, described surface treatment method is selected from one of following method:
A. active material (Si) is used diluted hydrofluoric acid (rare HF acid) solution-treated earlier, remove the SiO on surface 2, adopt plating bath deposition Cu at silicon face again, Fe, Ni or Cr particle are regulated the concentration and the sedimentation time of plating bath and can be controlled Cu, Fe, the content of Ni or Cr, THICKNESS CONTROL is in 1 nanometer-500 nanometer.
B. with active material Si and Cu, Fe, Ni or Cr be mechanical mixture according to a certain percentage, again through Overheating Treatment, perhaps with Si with contain Cu, Fe, the various salt of Ni or Cr are mechanical mixture according to a certain percentage, heat treatment in inert atmosphere at last.
C. active material Si is handled with rare HF acid solution earlier, remove the SiO on surface 2, adopt chemical hydrolysis (for example using the method for metatitanic acid four fourth fat hydrolysis) to coat one deck TiO on the surface 2Or Al 2O 3, THICKNESS CONTROL is in 1 nanometer-100 nanometer.Can reduce the solid electrolyte film (SEI film) and the negative reaction on Si surface so on the one hand, on the other hand can in and LiPF in the electrolyte 6Because the HF that the existence of minor amount of water generates.
D. prepare in position in the Si powder, for example utilizing SiH 4In the reduction preparation Si powder, adopt original position ald (ALD) bed process, at Si powder coated with uniform one deck TiO 2Or Al 2O 3Or Cu, Fe, Ni or Cr layer, THICKNESS CONTROL can prevent because nanometer Si surface ingress of air generates SiO like this in 1 nanometer-500 nanometer 2, reduce the side reaction in the follow-up battery system.
E. active material such as Si are put into the tube furnace of inert gas (as argon gas, hydrogen, nitrogen) protection and carbon source gas (as ethylene gas, acetylene gas, toluene vapor, benzene vapour etc.); (300～1200 ℃) at a certain temperature; heated 0.5 hour～15 hours; coat the C layer by chemical vapor deposition (CVD), coat THICKNESS CONTROL in 1 nanometer-100 nanometer.
If f. choose the less Si of yardstick (below 500nm), more SiO is contained on the surface 2, can be by generating Li with the inorganic matter that contains lithium (as lithium acetate, lithium carbonate, lithium hydroxide, lithium nitrate) reaction 2Si 2O 5, Li 2SiO 3, Li 4SiO 4, Li 8SiO 6Deng, reduce side reaction.
Can carry out the surface to active material by said method or other conventional method and coat processing.
(2) with above-mentioned at least a through in active material Si, Si oxide and the silicon alloy of surface treatment (also can without surface treatment), also can add the commodity material with carbon element, tin simple substance, one or more combinations in tin-oxide and ashbury metal, manganous oxide, the chromium oxide, organic precursor (carbon source is not particularly limited) with carbon containings such as pitch, resin, polyvinyl chloride, sucrose, starch, glucose, cyclodextrin, yellow starch gum, citric acids, acetylene black adds appropriate solvent according to a certain ratio and obtains uniform slurry by mechanical agitation; With the slurry spray drying of spray drying technology, obtain spherical precursor powder again with gained; Also can add mantoquita, in material, mix Cu after the cracking, improve conductivity of electrolyte materials in the slurry the inside.
(3) form pyrolytic carbon layer on inner composite particles surface
The spherical precursor powder that step (2) is obtained is (300～1200 ℃) heat treatment 0.5 hour～72 hours in certain temperature range under inert atmosphere (as argon gas, hydrogen, nitrogen), the organic precursor of above-mentioned carbon containing will be converted into RESEARCH OF PYROCARBON, and the surface that is coated on inner composite particles forms pyrolytic carbon layer, obtains the negative active core-shell material that the present invention is used for secondary lithium battery.
Following steps (4), (5), (6) are selectable method:
(4) at composite particles surface coverage CVD carbon-coating
The coating that step (3) is obtained the composite particles of pyrolytic carbon layer put into the tube furnace of inert gas (as argon gas, hydrogen, nitrogen) protection and carbon source gas (as organic gass such as methane, ethene, acetylene, benzene or toluene); (300～1200 ℃) at a certain temperature; heated 0.5 hour～72 hours, and utilized chemical vapour deposition (CVD) to coat one or more layers CVD carbon-coating again on the surface of the inside composite particles that has coated pyrolytic carbon layer.
After step (3) is handled, the pattern of the pyrolytic carbon layer of its surface coverage is relevant with the geometric shape of treatment conditions and inner composite particles, may be the skin covering of the surface that one deck evenly coats, also may be island or certain fluctuating carbon granule layer arranged, its coverage is not very high, and specific area is bigger.Through the further processing of step (4), can form equally distributed continuous carbon film on its surface, covered inner composite particles fully, reduce the specific area of whole composite particles.
(5) use spray drying technology to prepare the negative active core-shell material that the present invention is used for secondary lithium battery, also can be without step (4), directly coating particle surface deposition one deck Cu of pyrolytic carbon layer, THICKNESS CONTROL is in 1 nanometer-100 nanometer, at last at 100-1200 ℃, heat treatment in inert atmosphere or the reducing atmosphere (as argon gas, hydrogen, nitrogen).Allow Cu be diffused into material granule inside, increase conductivity, also can fuse between the Cu particle in addition, form network, the temperature of its concrete pattern and processing, speed, atmosphere and the heat treatment time of intensification are relevant.
(6) negative active core-shell material that is used for secondary lithium battery of the present invention that uses spray drying technology to prepare also can directly coat Al at the particle surface that coat pyrolytic carbon layer without step (4) and step (5) 2O 3Or TiO 2, can coat the TiO of 1 nanometer-100 nanometer at the core-shell material body structure surface as adopting metatitanic acid four fourth fat hydrolysis 2, perhaps also can adopt ald to coat one deck Al on the carbon-coating surface 2O 3, thickness can accurately be controlled, and the growth of the SEI film on negative material surface is relevant with active specific surface area size, adopts Al 2O 3, TiO 2Coating can these materials of passivation active surface, reduce the generation of SEI film, thereby improve coulombic efficiency first.
Use the spray drying method for preparation negative active core-shell material of secondary lithium battery that is used for of the present invention at step (2) preparation slurry, also can suitably add the mantoquita that is dissolved in coordinative solvent, through follow-up heat treatment, allow Cu, Fe, Ni or Cr are evenly distributed on the inside of nucleocapsid structure, increase the conductivity of material.
Use the spray drying method for preparation negative active core-shell material that is used for secondary lithium battery of the present invention, also can be without step (1), directly by step (2), (3), (4), (5), (6).
The preparation method who it is pointed out that the negative active core-shell material that is used for secondary lithium battery with above-mentioned The Nomenclature Composition and Structure of Complexes feature is not limited to said method, the visible accompanying drawing 1a of its architectural feature and Fig. 1 b.
Use the negative active core-shell material that is used for secondary lithium battery of above-mentioned spray drying preparation, the geometry appearance of its active material shape spherical in shape, it has higher tap density, lower specific surface.
(II) use chemical deposition to prepare the negative active core-shell material of M/Si of the present invention (M=Cu, Fe, Ni or Cr are the example explanation with Cu), comprise chemical gaseous phase ald and chemical liquid deposition.
1. chemical gaseous phase ald (ALD), chemical reactant in the ALD process (as trimethyl aluminium and aqueous vapor) are introduced reaction cavity with gaseous state at every turn, and arrive reactor with pulse mode.Reactant is by flow of sweep gas or bleed and disperse each other.Each reactant pulses is with particle surface generation chemical reaction, makes ALD to coat evenly simultaneously by this from limit procedure monolayer growth accurately.The ALD technology is very ripe technology in IC semiconductor technology, and we handle the coating that this technology applies to the powder electrode material, can comprise various metals, oxide, sulfide, nitride comprising material.The ALD that accompanying drawing 2 shows coats Al 2O 3Technological process.
Chemical gaseous phase ald (ALD) preparation M/Si (Ni or Cr are the example explanation with Cu for M=Cu, Fe) negative active core-shell material comprises the steps:
(1) selects suitable cupric predecessor, must satisfy following condition to choosing of cupric predecessor: 1) enough volatility are arranged, could be brought in the reaction cavity by carrier gas like this, and keep the certain reaction substrate concentration, the sufficient contact be arranged with the powder body material surface that coats; 2) enough thermal stabilitys are arranged, reaction source can not decomposed in the heated volatile process; 3) suitable reactivity is arranged, after being adsorbed in the hot surface of powder particle, can not decompose at once, need the participation reaction of next pulse reducing gas, could realize the accurate control of Cu film and evenly growth like this as the cupric predecessor.The cupric predecessor can be chosen the cuprous complex of amidino groups, and general general formula can be expressed as [(R ' NC (R) NR ") Cu] 2, (wherein, R ' and R " can be n-pro-pyl, isopropyl, normal-butyl, isobutyl group, Bai Dingji, the tert-butyl group etc.; R can be methyl, butyl etc.), for example be N, N-couple-isopropyl acetyl amidino groups copper, N; N-pair-sec-butyl acetyl amidino groups copper etc. also can choose stannous chloride (Cu 3Cl 3), beta-diketon copper (II) complex derivative, as cupric acetylacetonate, two (2,2,6,6 ,-tetramethyl-3, the acid of 5-heptadione) copper, hexafluoroacetylacetone acid copper etc.The reduction pulse gas can be chosen hydrogen, or formaldehyde.
(2) with silica-base material (particle size is excellent to be 300nm-4 μ m), put into reaction cavity, vacuumize heating, purpose is removed the aqueous vapor of cavity and material surface, and the temperature of reaction cavity finally is stabilized between 100-300 ℃.
(3) heating cupric predecessor, and utilize carrier gas (being preferably nitrogen) the cupric predecessor, hydrogen gas reactant is sent in the reaction cavity successively with the form of pulse.Can conditioned reaction thing pulsed dosage, the time of contact of reactant and powder, the blanking time between the pulse, the temperature of reaction cavity, the cycle-index of pulse waits controls sedimentary condition, and the powder that is coated utilizes the mobile mixing of air-flow that it is fully contacted with reactant.Final acquisition Cu/Si of the present invention is used for the secondary lithium battery cathode active material, and its structure is seen accompanying drawing 1c.
Adopt the chemical gaseous phase atomic layer deposition method to prepare the compound particle of Cu/Si nucleocapsid structure of the present invention, also can adopt ald (ALD) to coat some other metals, change its interfacial tension, perhaps oxide such as Al at the Si particle surface 2O 3, TiO 2, THICKNESS CONTROL is in 1 nanometer-100 nanometer.
2. chemical liquid deposition prepares M/Si of the present invention (Ni or Cr are the example explanation with Cu for M=Cu, Fe) negative active core-shell material step and comprises following steps:
(1) with commodity Si powder (particle size is 500nm-4 μ m) with rare HF acid preliminary treatment, remove the SiO on Si surface 2, also can suitably add some HNO 3Promote etching, allow Si particle surface roughening, at last solution is filtered.
(2) surface treated Si powder is joined contain Cu solution or PdCl 2, SnCl 2Activation Si surface in the solution also can be without surface active.
(3) will join in the plating bath that contains Cu through the Si powder of above-mentioned processing, choosing of plating bath do not had special requirement, as selecting to contain ethylenediamine tetraacetic ethyl disodium, copper chloride or copper sulphate or Schweinfurt green solution are made reducing agent with formaldehyde.Control reaction bath concentration, temperature, pH value, the reaction time can be controlled the coating thickness of Cu, and THICKNESS CONTROL is in 10 nanometers-100 nanometer.
(4) with the powder of gained Cu/Si nucleocapsid structure, in inertia or reducing atmosphere (as argon gas, hydrogen, nitrogen), heat treatment in 100 ℃-800 ℃ allows Cu diffuse into the Si granule interior on the one hand, increases conductivity.Also can fuse between the copper particle on the other hand.The pattern of copper layer is followed heating rate, heat treatment temperature, and heat treatment time, rate of temperature fall, heat treated atmosphere is relevant.
Obtain the Cu/Si composite material through above-mentioned chemical deposition; be necessary also can cover the CVD carbon-coating at particle surface; the particle of above-mentioned gained is put into the tube furnace of inert gas (as argon gas, hydrogen, nitrogen) protection and carbon source gas (as organic gass such as methane, ethene, acetylene, benzene or toluene); (300～1200 ℃) at a certain temperature; heated 0.5 hour～72 hours; utilize chemical vapour deposition (CVD) to coat one or more layers CVD carbon-coating again on the Cu/Si surface, its architectural feature is seen accompanying drawing 1d.
Obtain Cu/Si nucleocapsid composite material through above-mentioned chemical liquid deposition, also can utilize chemical hydrolysis or Atomic layer deposition method to coat one deck TiO on the surface 2Perhaps Al 2O 3, THICKNESS CONTROL is in 1 nanometer-100 nanometer.TiO 2Perhaps Al 2O 3Coating can the passivation particle surface active sites, reduce side reaction, improve efficient first.
It is pointed out that have above-mentioned The Nomenclature Composition and Structure of Complexes feature be used for the secondary lithium battery cathode active material can also adopt (III) Mechanical Method; (IV) hydro thermal method; (V) chemical vapour deposition technique prepares, and concrete preparation method can referenced patent: CN200410030990.X, CN200510082822.X, and the negative material method of preparation nucleocapsid structure is not limited to this.
The present invention also provides the electrode that comprises above-mentioned negative material and collector; Described collector can be the carrier of paper tinsel, net, porous body, foams or the corpus fibrosum material of various conductions, for example Copper Foil, nickel screen, nickel foam and carbon felt.
The preparation method of above-mentioned negative pole of the present invention is as follows:
Above-mentioned negative active core-shell material, binding agent, conductive additive are mixed according to a certain percentage, be coated on the carrier of paper tinsel, net, porous body, foams or corpus fibrosum material of various conductions (as Copper Foil, nickel screen, nickel foam, carbon felt etc.), in vacuum or inert atmosphere, 80-450 ℃, be preferably 120 ℃-350 ℃, more preferably heat-treat for 120 ℃-300 ℃, heat treatment time is 10 minutes-10 hours.The preparation method of anticathode is not particularly limited, for example can be with negative material, and conductive additive is dispersed in the solution that contains binding agent, mixes the slurry that obtains having certain viscosity, is coated on (for example Copper Foil) on the metal collector, and its structure is as shown in Figure 4.
The preparation of above-mentioned slurry, preferable methods is: binding agent is dissolved in the corresponding solvent, solvent can be done suitable selection according to compatibility, solvent composition is not particularly limited, for example can select N-N-methyl-2-2-pyrrolidone N-(NMP), N, dinethylformamide, N, N-dimethyl diacetayl amide etc.They can use separately, also can two or more be used in combination.Under the prerequisite that does not influence effect of the present invention, also can suitably add the additive that some promote polymerization reaction, perhaps add some and improve binding agent dissolubility and close-burning additive.
Among the preparation method of above-mentioned negative pole, binding agent is chosen the amide-type macromolecule, optimization aromatic polyamidoimide, aromatic polyamide, aromatic polyimide, and not one or more combinations of the presoma of polymerization fully.For example can incomplete amidated aromatic polyamide acid imide (containing amic acid in its medium chain) nmp solution will be contained, with compound particle, conductive additive mixes, be coated on the metal collector, in inert atmosphere or under the vacuum environment, 80-450 ℃, be preferably 120 ℃-350 ℃, more preferably heat-treat for 120 ℃-300 ℃, thereby make incomplete amidated polyamidoimide amidatioon, strand further increases, also can take place between the strand segment simultaneously crosslinked, thereby improve quality of forming film.Also can select to form the monomer (carboxylic acid or acid anhydrides and two amine components) of binding agent and can choose benzenetricarboxylic acid such as carboxylic acid or acid anhydrides, benzene tetracarboxylic acid, diphenyl tetracarboxylic dianhydride, PMDA, the diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride etc., two amine components can be chosen for diaminodiphenyl ether, phenylenediamine, ethylenediamine, propane diamine, 1,2 propane diamine, diethyl toluene diamine etc., acid anhydrides, the selection of the composition of diamines is not limited to this, with compound particle, conductive additive is mixed together and makes slurry, make its preliminary polymerization, be coated on the collector, then under inert atmosphere or vacuum environment, at 80-450 ℃, be preferably 120 ℃-350 ℃, 120 ℃ of-300 ℃ of heat treatments more preferably 10 minutes-10 hours make its polymerization film formation.Heat treated temperature can be selected according to the difference of binding agent.Accompanying drawing 3 has provided some amidatioons in various degree, the aromatic amides of imidizate, and acid imide molecule knot schematic diagram, the binding agent kind of employing is not limited thereto.
The coating of electrode is handled:
In the preparation of above-mentioned electrode, be coated on slurry on the collector after, also can adopt the method for chemical vapour deposition (CVD) such as ald (ALD) to coat one deck inorganic compound at electrode surface, the inorganic matter of coating can be Al 2O 3, TiO 2Deng, THICKNESS CONTROL is preferably 1 nanometer-20 nanometer in 1 nanometer-100 nanometer, inorganic compound coats the active sites that can reduce electrode, reduces the generation of side reaction, such as the generation that reduces the SEI film, improve enclosed pasture first efficient, the coating of inertia alkali compounds such as the Al in addition of battery 2O 3Also can be with electrolyte because the HF acid reaction that hydrolysis produces is avoided the electrode material structural damage.The control of thickness mainly is to avoid inorganic compound to influence the transmission of the electronics and the ion of negative pole.Accompanying drawing 5 is depicted as negative pole coats one deck inorganic compound through ald schematic diagram.Pole piece applies after the drying again that the advantage of coated inorganic compound is, inorganic matter be coated on the whole particle conductive network above, can not intercept whole conductive network, and then influence the transmission of pole piece electronics.The coating of inorganicization thing and the heat treatment of pole piece can be carried out simultaneously, also can coat after the first heat treatment.
Coat one deck inorganic compound about ald (ALD), with Al 2O 3Coating is described below for example: the above-mentioned pole piece for preparing is put into vacuum cavity, with water vapour, trimethyl aluminium is carrier gas with inert gas such as nitrogen, and circulation is gone in the vacuum cavity with the pulse pneumatic transmission successively, the vacuum cavity depositing temperature is controlled at 100-300 ℃, preferred 150-250 ℃.The hydrolysis of the monolayer by trimethyl aluminium, successively the particle surface at active material coats Al 2O 3, concrete principle is seen accompanying drawing 2, selects different organometallic sources for use, can coat different inorganic material, as TiO 2, Cu, Fe, Ni or Cr etc., ald coats evenly, it is accurately controlled to coat thickness.
The invention provides a kind of purposes of above-mentioned negative active core-shell material, this negative active core-shell material can be directly used in the negative material of secondary lithium battery.
The invention provides the purposes of another kind of above-mentioned negative active core-shell material, the existing negative material of this negative active core-shell material and other (as graphite) can be mixed, the negative material that is used for secondary lithium battery, wherein, described negative active core-shell material accounts for 3～98wt% of negative material total weight.
Negative active core-shell material with nucleocapsid structure provided by the invention, the change in volume of the active material of kernel in charge and discharge process is subjected to outer shell pyrolytic carbon layer, Cu, Fe, Ni or Cr layer, or the inhibition of CVD carbon-coating, even active material efflorescence in charge and discharge process also can keep good electrical contact with conductive additive all the time.
In addition, because the active material of kernel is by carbon-coating, Cu, Fe, Ni or Cr layer or Al 2O 3, TiO 2Coat, the growth of surface passivated membrane is only relevant with outer shell active sites area size, and the surface coating of outer shell is handled, and can significantly reduce the growth of passivating film.
For example adopt the CVD method at the carbon-coating that outside compound particle, coats one deck densification, reduce the compound particle specific area, the benefit of bringing like this is growth and the decomposition that passivating film has been avoided on inner active material surface, and the passivating film of outer surface can stable growth, and the lithium that consumes is few.Also can coat the Al of 1 nanometer-100 nanometer thickness at outer surface 2O 3, TiO 2Deng, can reduce the growth of passivating film like this, do not influence the electronics and the ion transport of material simultaneously again.
Adopt the amide-type high temperature resistant binder of high-tensile, high adherence, and adopt heat treatment method to prepare negative pole, guaranteed the long-time cyclical stability of negative pole.
Experimental results show that, coat processing by negative active core-shell material, the surface of adopting nucleocapsid structure, and adopt high performance amide-type high temperature resistant binder, made full use of and brought into play the big advantage of inner active material lithium storage content, solved the problem of change in volume, solved surface passivated membrane growth problem of unstable, so cyclicity and efficiency for charge-discharge significantly improve.In addition, the material of the inner active material of the conduct that the present invention adopts has the low characteristics of current potential that discharge and recharge, and therefore, adopts the secondary lithium battery of negative active core-shell material preparation of the present invention also to have the high advantage of energy density.
When the high power capacity negative active core-shell material of nucleocapsid structure of the present invention mixes the negative material that is used for secondary lithium battery with other existing negative material (as graphite), also can improve the electrochemical properties of this mixing negative material.For example the lithium storage content of graphite is 300～370mAh/g, the reversible capacity of a kind of silica-based composite particles negative material provided by the invention is 2300mAh/g, if these two kinds of materials are simply mixed, when silica-based composite particles negative material accounted for mixing negative material 20wt%, the reversible capacity of this mixing negative material can reach 730mAh/g; When silica-based composite particles negative material accounts for when mixing negative material 5wt%, this reversible capacity that mixes negative material is still up to 450mAh/g, all apparently higher than the lithium storage content of graphite.
The present invention also provides the secondary lithium battery that comprises above-mentioned negative pole, and the positive electrode active materials of this battery is the existing positive electrode that is used for secondary lithium battery, can reversibly embed and deviate from the transition metal oxide that contains lithium of lithium, for example LiCoO 2, LiNiO 2, LiMn 2O 4, LiFePO 4, LiNi 1-xCo xMnO 2Deng, and be not limited to this.
According to one embodiment of the invention, the preparation method of the positive pole of secondary lithium battery of the present invention is as follows: with positive electrode active materials, conductive additive (as acetylene black), binding agent (as the cyclohexane solution of 5% Kynoar) at normal temperatures and pressures, mixed in 85: 10: 5 by weight percentage and form the composite material slurries, it is coated on the aluminium foil as collector uniformly, the gained film thickness is 5 microns～40 microns, 100～150 ℃ of oven dry down, be 0.2～20Mpa/cm then at pressure 2Under compress, continue after the oven dry gained film to be cut into different shape by the prepared cell specification and to be positive pole 100～150 ℃ of bakings 12 hours.
The electrolyte of secondary lithium battery of the present invention can be organic electrolyte solution, can be added one or more solvable lithium salts by the mixed solvent that a kind of organic solvent or several organic solvent are formed and form.Typical organic solvent comprises: for example, vinyl carbonate (EC:ethylene carbonate), propylene carbonate (PC:propylene carbonate), diethyl carbonate (DEC:diethyl carbonate), dimethyl carbonate (DME:dimethyl carbonate), ethyl-methyl carbonic ester (EMC:ethylmethyl carbonate), dimethoxy-ethane (DME:dimethoxy-ethane) etc.; Typical solvable lithium salts comprises: for example, and LiClO 4, LiBF 4, LiPF 6, LiCF 3SO 3, LiAsF 6Deng; Typical system comprises: 1M LiPF for example 6(EC-DEC volume ratio 1: 1), 1M LiPF 6(EC-DMC volume ratio 3: 7) etc.In addition, can also in above-mentioned electrolyte, add various functional form additives, biphenyl for example, vinyl carbonic ester (VEC) etc.The selection of electrolyte also can be not limited to this.
The electrolyte of secondary lithium battery of the present invention also can be polymer dielectric, can adopt existing secondary lithium battery polymer dielectric, as polyethylene nitrile, LiClO 4, propylene carbonate and vinyl carbonate be with weight ratio 20: 5: 45: 30 mixtures of forming, or the mixture of the copolymer of Kynoar and hexafluoropropylene and lithium hexafluoro phosphate, and be not limited to this.
The barrier film that the barrier film of secondary lithium battery of the present invention is used for existing general secondary lithium battery, as the porous polypropylene barrier film, nonwoven fabrics, and be not limited to this.
Secondary lithium battery basic structure of the present invention is by containing the negative pole with compound particle of nucleocapsid structure as negative active core-shell material provided by the invention, contain the positive pole of the compound of lithium as positive electrode active materials, organic electrolyte solution or polymer dielectric, barrier film, collector, battery case, compositions such as lead-in wire.Wherein, separate by the barrier film that has soaked organic electrolyte solution or by polymer dielectric between positive pole and the negative pole, positive pole is burn-on respectively to go between with an end of negative pole and is linked to each other with the battery case two ends of mutually insulated.The profile of this secondary lithium battery can make button (individual layer) respectively, column type (multilaminate coiled), and square (multilayer folding), chewing gum type (multilayer folding) etc., and be not limited to this.
Secondary lithium battery of the present invention is applicable to that various mobile electronic devices maybe need the equipment of mobile driven by energy, mobile phone for example, notebook computer, portable video recorder, electronic toy, electric tool, electric automobile, hybrid vehicle, fields such as electric topedo, and be not limited to this.
Compare with the negative material of existing battery, the advantage of negative material of the present invention is: it is the core active material that negative material of the present invention has adopted the silica-based of high lithium storage content, and adopted special nucleocapsid structure, in addition, the present invention has adopted high-performance amide-type binding agent, and employing high-temperature heat treatment process, thereby, when this negative material is applied to the negative pole of secondary lithium battery, it is low to have the current potential of discharging and recharging, the reversible capacity height, and cyclicity is good, safe and reliable, the high remarkable advantage of first all coulombic efficiencies.
Description of drawings
Below, describe embodiments of the invention in conjunction with the accompanying drawings in detail, wherein:
Fig. 1 a is the compound particle schematic diagram of the nucleocapsid structure of employing spray drying preparation, wherein, 1: inner active material-silica-base material, 2: active material (as material with carbon element, manganese oxide, chromium oxide), 3: conductive additive or metallic particles, 4: coating layer (as: pyrolytic carbon layer, CVD carbon-coating, metal level, metal oxide layer); Fig. 1 b is the compound particle schematic diagram of the nucleocapsid structure of employing Mechanical Method preparation, wherein, and 1: inner active material, 2: pyrolytic carbon layer or conductive additive, 3: coating layer (as the CVD carbon-coating); M/Si (M=Cu, Fe, Ni or Cr) the compound particle schematic diagram of Fig. 1 c for adopting chemical deposition to prepare, wherein, 1: inner active material, 2: metal level; Fig. 1 d is the compound particle schematic diagram of C/M/Si (M=Cu, Fe, Ni or the Cr) nucleocapsid structure of the present invention's preparation, wherein, and 1: inner active material, 2: metal level, 3: coating layer (as pyrolytic carbon layer, CVD carbon-coating, metal level, metal oxide layer);
Fig. 2 is that ald (ALD) coats Al 2O 3Process chart, wherein, curved bars is represented particle surface;
Fig. 3 a is the amidated polyamidoimide molecular structure of part, wherein, and 1: amic acid structure, 2: imide structure; Fig. 3 b is a presoma polyamic acid molecular structure; Fig. 3 c is the polyimide molecule structure; Fig. 3 d is the polyamide molecular structure;
Fig. 4 is an electrode manufacturing process schematic diagram of the present invention;
Fig. 5 is the schematic diagram that adopts atomic layer vapour deposition (ALD) coated inorganic compound on pole piece, the inorganic compound layer that coats of the thick lines representative of below, the circular composite particles of representing;
Fig. 6 a and Fig. 6 b are different amplification ESEM scanning (SEM) photo of the carbon/silicon nucleocapsid compound particle of the employing embodiment of the invention 1 described spray drying method for preparation;
Fig. 7 is charging and discharging curve to 5 weeks before the electrode for carbon/silicon nucleocapsid compound particle of adopting the embodiment of the invention 1 preparation with lithium metal, and wherein, efficient is 80% first;
Fig. 8 is for adopting the carbon/silicon nucleocapsid structure compound particle cyclicity curve (2V-5mv) of the embodiment of the invention 1 preparation;
Fig. 9 is for adopting the carbon/silicon nucleocapsid structure negative material deboost cyclicity curve (2V-110mV) of the embodiment of the invention 1 preparation;
Figure 10 a and Figure 10 b are the SEM photo of the carbon/silicon nucleocapsid structure compound particle different amplification of the employing embodiment of the invention 2 preparations;
Figure 11 is for adopting the carbon/silicon nucleocapsid structure negative material deboost cyclicity curve (2V-110mV) of the embodiment of the invention 2 preparations;
Figure 12 a is the SEM photo of raw material Si in the embodiment of the invention 8, and wherein particle size is the 1-4 micron; Figure 12 b is the SEM photo of the embodiment of the invention 8 after evenly coating Cu on the Si; Figure 12 c is under inert atmosphere protection, through the surface topography of 250 ℃ of heat treated Cu; Figure 12 d is the section S EM photo of ion beam etching Cu/Si core-shell material;
Figure 13 is the charging and discharging curve of the ALD subsequent treatment of the electrode process embodiment of the invention 16 of the core-shell material making of the employing embodiment of the invention 1 preparation, and wherein, efficient is 84% first, has improved 4%.
Embodiment
Embodiment 1 uses spray drying method for preparation to contain the negative active core-shell material I of silicon
(1) with the commodity Si (granularity is 500 nanometers) of drying, (granularity is the 1-15 micron to the commodity material with carbon element, material with carbon element can be carbonaceous mesophase spherules MCMB, native graphite, Delanium), as the carbon black (average grain diameter is 40 nanometers) of conductive additive, phenolic resins, 1: 2: 0.4 by weight: 1 proportioning added in the ethanolic solution, evenly mixed obtaining having certain density slurry (also can not add conductive additive);
(2) the above-mentioned slurry usefulness spray dryer that obtains is descended the dry spherical precursor powders that get at 70 ℃, dry gas can be compressed air or inert gas, and the flow of dry gas is 10L/min, and compressed air pressure is 7bar, and the flow of slurry is 300ml/h;
(3) the spherical precursor powder that step (2) is obtained, pyrolysis under high pure nitrogen, the method of pyrolysis is: be warmed up to 400 ℃ with 4 hours from room temperature earlier, be warmed up to 900 ℃ with 5 hours from 400 ℃ again, then at 900 ℃ of constant temperature after 10 hours, dropped to room temperature with 2 hours at last, obtained coating the spherical composite pellets of pyrolytic carbon layer, the granularity particle diameter is at the 10-30 micron;
(4) (volume ratio is 1: 4 under the mist that contains toluene and high pure nitrogen, flow is 200ml/ minute, the tube furnace volume is 0.02 cubic metre), (method for pyrolysis is: be raised to 800 ℃ with 5 hours from room temperature earlier with the 800 ℃ of pyrolysis in tube furnace of above-mentioned spherical composite pellets, 800 ℃ of constant temperature 2 hours, again with dropping to room temperature in 2 hours), obtain the negative active core-shell material I that is used for secondary lithium battery of the present invention, the weight ratio of its each several part is listed in table 1.
In order to study the chemical property that uses secondary lithium battery negative active core-shell material of the present invention, below will adopt an Experimental cell to study.
Experimental cell is at H 2Assemble in the argon filling glove box of O content＜1.0ppm.
The electrolyte of Experimental cell is 1M LiPF 6Be dissolved in the mixed solvent of vinyl carbonate and dimethyl carbonate (volume ratio is 1: 1).
The preparation of the negative pole of Experimental cell: the negative active core-shell material I and the conductive black that are used for secondary lithium battery that will contain Si and material with carbon element, complete solution (the similar Fig. 2 a of its molecular structure of the polyamidoimide of polymerization not, solvent is a N-methyl 2-Pyrrolidone), mix at normal temperatures and pressures and form slurry (oven dry back three's weight ratio is 85: 5: 10), evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～50 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue that heat treatment made its cross-linked polymeric in 1 hour in 250 ℃ of inert atmospheres, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The preparation of the positive pole of Experimental cell: with LiMn 2O 4Powder and conductive black, the cyclohexane solution of 5%PVDF mix and form slurry (weight ratio after three's oven dry is 85: 10: 5), evenly are coated on the aluminum substrates as anodal coating, obtain thickness and be 5～40 microns film; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down, after this film is cut to area is 1cm 2Thin rounded flakes as the positive pole of Experimental cell.
With other basic building block except that electrolyte or solid electrolyte of Experimental cell, in the argon filling glove box, be assembled into Experimental cell according to a conventional method as dryings such as negative pole, positive pole, barrier film, collector, battery case, lead-in wire back.
Use is subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles to test, and the current density of test is 0.4mA/cm 2, the charging cut-ff voltage is 4.25V, and discharge cut-off voltage is 2V, and test result is listed in table 1.
Use is studied the discharge characteristics of composite negative pole material of the present invention with respect to lithium metal by the simulated battery of composite negative pole and lithium assembling, simulated battery be metallic lithium foil to electrode, the current density of charge and discharge cycles test is 0.4mA/cm 2, the charging cut-ff voltage is 2V, discharge cut-off voltage is 0.0V.For the higher active negative pole of capacity, can adopt the mode of deboost, help improving cyclicity.The material structure feature of embodiment 1 preparation as shown in Figure 6, the charging and discharging curve of simulated battery as shown in Figure 7, the cyclicity curve of simulated battery such as Fig. 8 and shown in Figure 9, test result is listed in table 1.
Embodiment 2 uses spray drying method for preparation to contain the negative active core-shell material II of silicon
(1) with the commodity Si (particle mean size is in 500 nanometers) of drying, conductive carbon black (average grain diameter 30 nanometers), phenolic resins are pressed 10: 0.5: 3 proportionings and are added in the ethanolic solution, evenly mix obtaining having certain density slurry;
(2) the above-mentioned slurry that obtains is got spherical precursor powder at 80 ℃ with compressed air drying with spray dryer, the flow 8L/min of dry gas, compressed air pressure are 6bar, and the flow of slurry is 250ml/h;
(3) with the spherical precursor powder of step (2) gained, pyrolysis under high pure nitrogen, the method of pyrolysis is: be warmed up to 400 ℃ with 4 hours from room temperature earlier, be warmed up to 800 ℃ with 5 hours from 400 ℃ again, then at 800 ℃ of constant temperature after 10 hours, drop to room temperature with 2 hours at last, obtained coating the spherical composite pellets of pyrolytic carbon layer;
(4) (volume ratio is 1: 4 under the mist that contains acetylene and high pure nitrogen, flow is 200ml/ minute, the tube furnace volume is 0.02 cubic metre), (method for pyrolysis is: be raised to 800 ℃ with 4 hours from room temperature earlier with the 800 ℃ of pyrolysis in tube furnace of above-mentioned spherical composite pellets, 800 ℃ of constant temperature 3 hours, again with dropping to room temperature in 2 hours), obtain the negative active core-shell material II that is used for secondary lithium battery of the present invention, the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: the nmp solution of the active material II and 10% polyamide (molecular structure is Fig. 2 d for example) of above-mentioned preparation is mixed the formation slurry at normal temperatures and pressures, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
Positive pole preparation, assembling and the method for testing of Experimental cell are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, but charging/discharging voltage is limited in 0.12V-2V, and its test result is listed in table 1.The material structure feature is shown in Figure 10, the cyclicity curve of simulated battery as shown in figure 11, test result is listed in table 1.
Embodiment 3 uses spray-on process to prepare the negative active core-shell material III of C/Cu/Si
(1) with Si (average grain diameter is 1 micron), Schweinfurt green,, phenolic resins joins in 10: 2: 3 ratio and is mixed with slurry (also can add a certain amount of conductive additive) in the alcohol solvent;
(2) above-mentioned made slurry usefulness spray dryer is descended the dry spherical precursor powders that get at 80 ℃, the flow 15L/min of dry gas, compressed air pressure are 8bar, and the flow of slurry is 400ml/h;
(3) the spherical precursor powder that step (2) is obtained is heat-treated under high pure nitrogen, and heat-treating methods is: be warmed up to 700 ℃ with 2 hours from room temperature earlier, at 700 ℃ of constant temperature after 1 hour, dropped to room temperature with 2 hours again, obtain containing Si, the Cu composite particles;
(4) (volume ratio is 1: 4 under the mist that contains ethene and high pure nitrogen, flow is 200ml/ minute, the tube furnace volume is 0.02 cubic metre), with the above-mentioned Si that contains, (method for pyrolysis is the 700 ℃ of pyrolysis in tube furnace of Cu compound particle: be raised to 700 ℃ with 3 hours from room temperature earlier, 700 ℃ of constant temperature 5 hours, again with dropping to room temperature in 2 hours), obtain the negative active core-shell material III that is used for secondary lithium battery of the present invention, this negative active core-shell material has nucleocapsid structure, and average diameter is 15 microns, and active material Si and Cu are contained in its inside, outermost layer has coated and has utilized the carbon-coating of CVD from ethylene pyrolysis, and the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: (1) will contain negative active core-shell material III that is used for secondary lithium battery and the monomer PMDA of C/Cu/Si, phenylenediamine (monomer mole ratio 1: 1, the mass ratio of active material and monomer is 10: 1) join mixed slurry in the N-methyl 2-Pyrrolidone solvent, be coated on the Cu collector, obtain the film that thickness is the 2-20 micron;
(2) with this film at 60-80 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continued under 300 ℃ of inert atmospheres or vacuum environment heat treatment 1 hour, make its polymerization crosslinking complete, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test class are with embodiment 1, and its test result is listed in table 1.
Embodiment 4 uses spray drying method for preparation to contain the negative active core-shell material IV of Si
(1) with commodity Si (average diameter is at the 1-2 micron), with multi-walled carbon nano-tubes (draw ratio is 100: 1, and length is 20 microns, wall thickness 5 nanometers) as conductive additive, the asphalt powder of pure dissolubility join at 9: 1: 2.5 in proportion in the ethanolic solution mix slurry;
(2) the above-mentioned slurry that obtains is prepared spherical precursor powder with spray dryer, drying parameter is analogous to embodiment 1;
(3) with the spherical precursor powder of gained, pyrolysis under high pure nitrogen, the method of pyrolysis is: be warmed up to 500 ℃ with 3 hours from room temperature earlier, be warmed up to 1000 ℃ with 5 hours from 500 ℃ again, then at 1000 ℃ of constant temperature after 10 hours, drop to room temperature with 2 hours at last, obtained coating the spheric granules of pyrolytic carbon layer;
(4) with this spheric granules, (volume ratio is 1: 4 under the mist that contains ethene and high pure nitrogen, flow is 200ml/ minute, the tube furnace volume is 0.02 cubic metre), (method for pyrolysis is: be raised to 800 ℃ with 7 hours from room temperature earlier in 800 ℃ of pyrolysis in tube furnace, 800 ℃ of constant temperature 4 hours, again with dropping to room temperature in 2 hours), obtain the negative active core-shell material IV that is used for secondary lithium battery of the present invention, this negative active core-shell material has nucleocapsid structure, the composite particles of active material Si and multi-walled carbon nano-tubes composition is contained in its inside, its outside has coated the carbon granule layer from asphalt pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from ethylene pyrolysis, and outer dia is 50 microns, and the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: the secondary lithium battery cathode active material IV that is used for that will contain Si mixes the formation slurry at normal temperatures and pressures with the nmp solution of 10% polyamide (molecular structure such as Fig. 2 c), evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The preparation of the positive pole of Experimental cell, Experimental cell assembling and method of testing be with embodiment 1, and the assembling of simulated battery and test be with embodiment 1, deboost (130mv-2V), and its test result is listed in table 1.
Embodiment 5 uses spray drying method for preparation to contain the negative active core-shell material V of silicon
(1) with the commodity silica flour (granularity is 300nm) of drying and carbon black (average grain diameter is 10 nanometers) as conductive additive, the superfine graphite powder, sucrose is in 10: 0.1: 20: 5 ratios water-soluble mixed must slurry;
(2) slurry is prepared spherical precursor powder with spray-dired method, drying parameter is analogous to embodiment 1;
(3) should the sphere precursor powder, pyrolysis under high pure nitrogen, the step of pyrolysis is: be warmed up to 400 ℃ with 4 hours from room temperature earlier, be warmed up to 900 ℃ with 10 hours from 400 ℃ again, then at 900 ℃ of constant temperature after 12 hours, drop to room temperature with 2 hours at last, obtained coating the inside composite particles of pyrolytic carbon layer;
(4) (volume ratio is 1: 5 under the mist that contains toluene and high pure nitrogen, flow is 100ml/ minute, the tube furnace volume is 0.02 cubic metre), the 900 ℃ of pyrolysis in tube furnace of above-mentioned composite particles (were raised to 900 ℃ with 2 hours from room temperature earlier, 900 ℃ of constant temperature 5 hours, again with dropping to room temperature in 2 hours), obtain the negative active core-shell material V that is used for secondary lithium battery of the present invention, this negative active core-shell material has nucleocapsid structure, the composite particles of active material silicon and conductive black composition is contained in its inside, its outside has coated the carbon granule layer from the starch pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, outer dia is 10 microns, and the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: what will contain silicon is used for secondary lithium battery cathode active material V and 5% conductive carbon black, the nmp solution of 10% polyamidoimide (molecular structure such as Fig. 2 c) mixes formation slurry (weight ratio after three's oven dry is 85: 5: 10) at normal temperatures and pressures, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continued in 250 ℃ of inert atmospheres heat treatment 2 hours, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
Embodiment 6 uses spray drying method for preparation to contain the negative active core-shell material VI of C/Cu/Si
(1) with the Si (granularity is 300nm) of commodity, adds the CuCl that 0.03mol/L contains rare HF (concentration is 0.5%) 2In the solution, stir filtration in 40 minutes, wherein, add HF and be in order to go out the SiO on Si surface 2, add CuCl 2Be at Si surface deposition seed crystal, activate the Si surface;
(2) with CuCl 2, (1: 2-4) proportioning is added to the water and obtains the plating bath of 0.03mol/L concentration ethylenediamine tetraacetic ethyl disodium (EDTA) in molar ratio;
(3) join in the above-mentioned plating bath at the Si powder that step (1) is obtained, the weight of silica flour and Cu proportioning can be chosen 4 parts of silica flours, 2 parts of CuCl 2, bath concentration is 0.03mol/L, and concentration of formaldehyde is 15ml/L, and regulating pH value be between the 7-13, preferred 12, stirring 10min-2h, filtration can obtain the Si powder that is coated by Cu;
(5) follow-up method be analogous to embodiment 2, spray drying, heat treatment, CVD coats and obtains the negative active core-shell material VI that is used for secondary lithium battery of the present invention that obtains of the present invention, this negative active core-shell material has nucleocapsid structure, active material Si and Cu are contained in (outer dia is 30 microns) its inside, and its outside has coated the carbon granule layer from the resin pyrolysis, and the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: the secondary lithium battery cathode active material VI that is used for that will contain Si mixes the formation slurry at normal temperatures and pressures with 10% polyimides (molecular structure such as Fig. 1 c) nmp solution, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 300 ℃ of oven dry 1 hour down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The preparation of the positive pole of Experimental cell,, Experimental cell assembling and method of testing be with embodiment 1, the assembling of simulated battery and test are with embodiment 1, its test result is listed in table 1.
Embodiment 7 uses spray drying method for preparation to contain the negative active core-shell material VII of Si
(1) with the Si (particle mean size is 500nm) of commodity, add and contain in the water and ethanolic solution of rare HF (concentration is 0.5%), the ratio of water and ethanol is 1: 1, stirs filtration in 40 minutes.Add HF and be in order to go out the SiO on Si surface 2, the adding of ethanol is for the Si powder better being disperseed, can certainly adding some surfactant additives and promote the dispersion of Si powder at the aqueous solution;
(2) above-mentioned solution is filtered, the powder of obtaining is joined (consumption adds the ratio of 20ml metatitanic acid four fourth fat in the 1g silica flour) in the ethanolic solution that contains metatitanic acid four fourth fat, stirred 30 minutes, and dripped the aqueous solution that 30ml contains glacial acetic acid, wherein the aqueous solution and glacial acetic acid volume ratio are 1: 1.Add glacial acetic acid and promote on the one hand the hydrolysis of metatitanic acid four fourth fat can not cause react fierce excessively by force because of acidity on the other hand, cause coating inhomogeneous, filtration at last obtains precursor powder.
(3) with above-mentioned gained precursor powder, follow-up processing procedure is with embodiment 2, spray drying, heat treatment, CVD coats and obtains the negative active core-shell material VII that is used for secondary lithium battery of the present invention that obtains of the present invention, this negative active core-shell material has nucleocapsid structure, and TiO is contained in (outer dia is 50 microns) its inside 2The active material Si that coats, its outside has coated the carbon granule layer from the resin pyrolysis, and the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: the secondary lithium battery cathode active material IV that is used for that will contain Si mixes the formation slurry at normal temperatures and pressures with 10% polyimides (molecular structure such as Fig. 1 b) nmp solution, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 80 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 250 ℃ of oven dry 1.5 hours down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The preparation of the positive pole of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are identical with embodiment 1, deboost 80mv-2V wherein, and it discharges and recharges and the results are shown in subordinate list 1.
Embodiment 8 uses spray drying method for preparation to contain the negative active core-shell material VIII of silicon
The preparation method is analogous to embodiment 1, just changes silicon/commodity material with carbon element content into 1: 1, makes the lithium ion battery negative VIII that spherical nucleocapsid of the present invention is used for secondary cell, and the weight ratio of each several part is listed in table 1.Electrode preparation and battery testing are similar to embodiment 1.
Embodiment 9 uses spray drying method for preparation to contain the negative active core-shell material IX of silicon
The preparation method is analogous to embodiment 1, just changes silicon/commodity material with carbon element content into 2: 1, makes the lithium ion battery negative IX that spherical nucleocapsid of the present invention is used for secondary cell, and the weight ratio row and the test result of its each several part see Table 1.Electrode preparation and battery testing are similar to embodiment 1.
Embodiment 10 uses spray drying method for preparation to contain the negative active core-shell material X of silicon
The preparation method is analogous to embodiment 1, just changes Si/ commodity material with carbon element content into 3: 1, makes the lithium ion battery negative X that spherical nucleocapsid of the present invention is used for secondary cell, and the weight ratio row and the test result of each several part see Table 1.Electrode preparation and battery testing are similar to embodiment 1.
Embodiment 11 uses spray drying method for preparation to contain the negative active core-shell material XI of silicon
The preparation method is analogous to embodiment 1, just changes Si/ commodity material with carbon element content into 4: 1, makes the lithium ion battery negative XI that spherical nucleocapsid of the present invention is used for secondary cell, and the weight ratio row and the test result of its each several part see Table 1.Electrode preparation and battery testing are similar to embodiment 1.
What need proposition is that the ratio of Si and commodity material with carbon element is not limited to this.
Embodiment 12 uses the negative active core-shell material XII of electronation deposition preparation Cu/Si nucleocapsid structure
(1), handled in advance 10 minutes with HF (concentration is 0.5-5%) with commodity Si (granularity is the 1-4 micron).Also can suitably add HNO 3, HF: HNO 3Ratio can be 2: 1, and the adding of HNO3 can promote the corrosion of Si, makes smooth silicon face produce small stair, helps the even coating of Cu particle;
(2) above-mentioned surface treated Si powder is joined contain rare HF (concentration is 0.5%) CuCl 2In the solution, CuCl 2Solution concentration is 0.03mol/L, stirs filtration in 20 minutes, wherein, adds HF and is in order to go out the SiO on Si surface 2, add CuCl 2Be at Si surface deposition seed crystal, activate the Si surface, also can adopt PdCl 2Or SnCl 2Solution activation Si particle surface;
(3) with CuCl 2, ethylenediamine tetraacetic ethyl disodium (EDTA) in molar ratio (1: 2-4) the proportioning plating bath of the concentration that obtains 0.03mol/L that is added to the water, the silica flour that step (1) is obtained joins in the plating bath, the weight of silica flour and Cu proportioning can be chosen 4 parts of silica flours, 4 parts of CuCl 2, concentration of formaldehyde is 15ml/L, regulating pH value be between the 7-13, preferred 12, and stirring 10min-2h, filtration can obtain the Si powder that is coated by Cu;
(4) powder of above-mentioned acquisition is heat-treated for 100-800 ℃ at inert atmosphere (as argon gas, nitrogen, argon hydrogen gaseous mixture).Obtain the negative active core-shell material XII that is used for secondary lithium battery of the present invention, this negative active core-shell material kernel is Si, skin is Cu, and the thickness of Cu layer can be controlled between 10 nanometers-100 nanometer according to the concentration and the sedimentation time of plating bath, and its architectural feature as shown in figure 12.
The preparation of the negative pole of Experimental cell: what will contain Cu/Si is used for secondary lithium battery cathode active material VIII and conductive carbon black, the nmp solution of 15% polyamidoimide mixes formation slurry (weight ratio after three's oven dry is 80: 5: 15) at normal temperatures and pressures, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continued under 250 ℃ of inert atmospheres heat treatment 1 hour, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
It is to be noted that the method for chemical solution deposition Cu layer is not limited to this, the selection of plating bath is not limited to this.
Embodiment 13 uses the negative active core-shell material of electronation deposition preparation Ni/Si nucleocapsid structure
(1) with the Si (granularity is the 1-4 micron) of commodity, handled in advance 15 minutes with HF (concentration is 0.5-5%).Also can suitably add HNO 3, HF: HNO 3Ratio can be 1: 1, HNO 3Adding can promote the corrosion of Si, make smooth silicon face produce small stair, help the even coating of Ni particle;
(2) above-mentioned surface treated Si powder is joined in the nickeliferous acidic bath, plating bath can be chosen for nickelous sulfate (25g/L), and hypophosphorous acid is received (25g/L), acetic acid is received (12g/L), lactic acid (28ml/L), and regulating the pH value is 4.5, depositing temperature is 70 ℃, stirs 30min-2h.Filter.
Follow-up heat treatment is analogous to embodiment 12.Electrode is made, the battery assembling, and test class is same as embodiment 12.
Embodiment 14 uses the negative active core-shell material of electronation deposition preparation Cr/Si nucleocapsid structure
(1) processing on Si surface is analogous to embodiment 13.
(2) the treated Si powder in surface is joined PdCl 2Carry out surface active, PdCl in the dilute hydrochloric acid solution 2Concentration is 1g/L.
(3) will join Cr through the Si powder of above-mentioned processing 2(SO 4) 36H 2O (0.1mol/L), NaH 2PO 2H 2O (0.1mol/L), KCNS (0.1-0.2mol/L), regulating the pH value is 3.0, depositing temperature is 50 ℃, stirs to be 30min-2h.Filter.
Follow-up heat treatment is analogous to embodiment 12.Electrode is made, the battery assembling, and test class is same as embodiment 12.
Embodiment 15 uses the iron negative active core-shell material that is equipped with the Fe/Si nucleocapsid structure of chemical deoxidizing plating
(1) processing on Si surface is analogous to embodiment 13.
(2) will join through the Si powder of above-mentioned processing and contain Fe 2+Plating bath in, the composition of plating bath, deposition step be embodiment 12 roughly the same, just with CuCl 2Be changed to FeCl 2, can be by the even Si powder that coats of Fe.
Follow-up heat treatment is analogous to embodiment 12.Electrode is made, the battery assembling, and test class is same as embodiment 12.
The selection that it is pointed out that plating bath among the embodiment 12-15 is not limited to this.Also can select to mix plating bath, select multiple metal deposition to coat, following embodiment 16 is described.
Embodiment 16 uses the negative active core-shell material of electronation deposition preparation Cu-Ni/Si nucleocapsid structure
(1) processing on Si surface is analogous to embodiment 13.
(2) will join through the Si powder of above-mentioned processing and contain NiSO 46H 2O (0.6mol/L), CuSO 45H 2O (0.4mol/L), NaH 2PO 2H 2O (0.28mol/L), C 6H 5Na 3O 72H 2O (0.2mol/l) and CH 3COONH 4(0.5mol/L) in the plating bath of Zu Chenging, regulating the pH value is 4.5, and depositing temperature is 50 ℃, stirs 10min-2h, filters to obtain the even Si powder that coats by Cu-Ni.
Follow-up heat treatment is analogous to embodiment 12. electrodes and makes, the battery assembling, and test class is same as embodiment 12.
It may be noted that multiple metallic cover method is not limited to this.
Embodiment 17 uses ald to prepare Cu/Si nucleocapsid structure negative active core-shell material
(1) Si (granularity is the 1-4 micron) with commodity puts in the reaction cavity, vacuumizes and is heated to 200 ℃, and chamber pressure is approximately 10 -2Torr utilizes nitrogen current that system is degassed, and purpose is away the aqueous vapor of cavity and powder surface;
(2) heating cupric precursor source (as choosing N, N-pair-sec-butyl acetyl amidino groups copper) makes its temperature stabilization at 80 ℃. and heating reaction cavity temperature makes it maintain 200 ℃;
(3) open cupric predecessor and Ar/H 2(8%) gas source is provided with the deposition program, and the deposition program mainly comprises following parameter, N, the pulsed dosage (can establish 0.05s) of N-pair-sec-butyl acetyl amidino groups copper, Ar/H 2Pulsed dosage (can establish 0.05s), utilize nitrogen to be carrier gas, send into it in reaction cavity successively, carrier gas flux is 20sccm, be pulse spacing (can establish 5s) time of contact of reaction source and powder, cycle-index (can be provided with 500 times), the thickness of each cyclic deposition is 1.5A °/cycle, the Cu thickness of deposition is about 75nm;
(4) finish deposition and take out sample, obtain the negative active core-shell material that is used for secondary lithium battery of the present invention, this negative active core-shell material has nucleocapsid structure, and active material silicon is contained in its inside, and its outside has evenly coated the continuous Cu layer of 75nm
The preparation of the negative pole of Experimental cell: with negative electrode active material that is used for secondary lithium battery and the conductive carbon black of the above-mentioned Cu/Si of containing, 10% not fully the nmp solution of the polyamidoimide of imidizate mix at normal temperatures and pressures and form slurry (weight ratio after three's oven dry is 85: 5: 10), evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 200 ℃ of oven dry 2 hours down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
The cupric precursor source of this example is not limited to N, N-pair-sec-butyl acetyl amidino groups copper, can choose the cuprous complex of amidino groups, general general formula can be expressed as [(R ' NC (R) NR ") Cu] 2, (R ' and R " can be n-pro-pyl, isopropyl, normal-butyl, isobutyl group, Bai Dingji, the tert-butyl group etc., R can be methyl, butyl etc.), as N, N-pair-isopropyl acetyl amidino groups copper, N, N-pair-sec-butyl acetyl amidino groups copper etc. also can be chosen cuprous halide (as Cu 3Cl 3), beta-diketon copper (II) complex derivative, as cupric acetylacetonate, two (2,2,6,6 ,-tetramethyl-3, the acid of 5-heptadione) copper, hexafluoroacetylacetone acid copper etc.The heating-up temperature setting in cupric forerunner source can be selected according to the physical characteristic of compound.The reducing gases body source is not limited to H 2, also can select formaldehyde etc.
Embodiment 18 preparations contain the negative pole of C/Cu/Si nucleocapsid structure
Wherein the preparation of Cu/Si nucleocapsid structure material is similar to embodiment 12, can adopt the CVD step that is similar to embodiment 1 subsequently, coat continuous carbon-coating on Cu/Si material granule surface, obtain the C/Cu/Si nucleocapsid composite material that is used for secondary lithium battery of the present invention.Each several part mass ratio and test structure see Table 1.
Embodiment 19 preparations contain the negative pole of C/Cu/Si nucleocapsid structure
The preparation of Cu/Si nucleocapsid structure material can the described method of similar patent CN200510082822.X prepare, and adopts the mechanical ball milling method, adopts silica flour, carbonaceous organic material, the predecessor of cupric or copper powder ball milling, the preparation of Cu powder also can be directly adopted in pyrolysis preparation in inert atmosphere then.The parameter of cracking is similar noted earlier.Obtain the C/Cu/Si nucleocapsid composite material that is used for secondary lithium battery of the present invention.Each several part mass ratio and test structure see Table 1.
Embodiment 20 uses spray drying method for preparation to contain the negative active core-shell material of Si
Commodity Si (particle mean size 200-300 nanometer) with drying, lithium acetate or lithium nitrate are as the carbon black (average grain diameter is 40 nanometers) of conductive additive, phenolic resins, add in the ethanolic solution by 5: 0.4: 3.4 proportionings, evenly mix obtaining having certain density slurry.Spherical precursor powder preparation, thermal cracking, CVD coats carbon-coating and is similar to embodiment 1.The purpose that adds lithium acetate or lithium nitrate is because of at high temperature lithium acetate or lithium nitrate decompose the Li that produces 2The SiO on O meeting and nanometer Si surface 2Reaction generates Li 2Si 2O 5, Li 2SiO 3, Li 4SiO 4, or Li 8SiO 6, reduce the generation of follow-up pole piece side reaction, thereby improve enclosed pasture efficient first, product and SiO 2And Li 2The O ratio is relevant with reaction temperature, can be according to SiO 2And Li 2The O binary phase diagraml is determined reaction ratio and reaction temperature.
The preparation of the negative pole of Experimental cell: the above-mentioned Si of containing is used for secondary lithium battery cathode active material and conductive carbon black, the nmp solution of the polyamidoimide of imidizate does not mix formation slurry (weight ratio after three's oven dry is 85: 5: 10) at normal temperatures and pressures fully, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 270 ℃ of heat treatments 1 hour, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
Embodiment 21 uses spray drying method for preparation to contain the negative active core-shell material of Si
(1) with dry commodity Si (50nm) and LiCl, citric acid is dissolved in ethanol in proportion at 2: 1.6: 2.6, with the ethanol evaporate to dryness, obtains containing the collosol and gel of silica flour;
(2) with the gained collosol and gel in inert atmosphere (as nitrogen, argon gas) heat treatment, heat treated step is: be warmed up to 300 ℃ with 3 hours from room temperature earlier, constant temperature 2 hours, be warmed up to 800 ℃ with 4 hours from 300 ℃ again, after 5 hours, drop to room temperature with 2 hours at 800 ℃ of constant temperature at last then, obtain the Si nano particle that lithium metasilicate coats.Step subsequently is analogous to embodiment 2, and spray drying prepares spherical precursor powder, thermal cracking, and CVD coats carbon-coating.Obtain the negative active core-shell material that is used for secondary lithium battery of the present invention at last, this negative active core-shell material has nucleocapsid structure, the composite particles that the active material Si that coated by lithium metasilicate and acetylene black are formed is contained in its inside, its outside has coated the carbon granule layer from asphalt pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, outer dia is 1 micron, and the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: the above-mentioned Si of containing is used for secondary lithium battery cathode active material and conductive carbon black, (molecular structure such as Fig. 2 be nmp solution a) for the polyamidoimide of complete polymerization, mix at normal temperatures and pressures and form slurry (weight ratio after three's oven dry is 85: 10: 5), evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 260 ℃ of following heat treatments 2 hours, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and wherein voltage limit is 100mv-2V, and its test result is listed in table 1.
Embodiment 22 uses spray drying method for preparation to contain the negative active core-shell material active material of Si-MnO
(1) preparation Si-MnO nucleocapsid compound particle step is analogous to embodiment 1, commodity Si (particle mean size 200-300 nanometer) with drying, MnO (granularity is 500nm), carbon black (average grain diameter is 40 nanometers) as conductive additive, phenolic resins, by 1: 2: 0.4: 1 proportioning added in the ethanolic solution, and even mixing obtains having certain density slurry and (also can not add conductive additive;
(2) the above-mentioned slurry that obtains is got spherical powder with spray dryer, drying parameter is embodiment 1 roughly the same, and granularity is controlled at 20 microns;
(3) with the spherical presoma of gained, pyrolysis under high pure nitrogen, the step of pyrolysis is: be warmed up to 400 ℃ with 4 hours from room temperature earlier, be warmed up to 600 ℃ with 5 hours from 400 ℃ again, then at 600 ℃ of constant temperature after 10 hours, drop to room temperature with 1 hour at last, obtained coating the spheric granules of pyrolytic carbon layer;
(4) (volume ratio is 1: 4 under the mist that contains toluene and high pure nitrogen, flow is 200ml/ minute, the tube furnace volume is 0.02 cubic metre), the 600 ℃ of pyrolysis in tube furnace of this composite particles (were raised to 600 ℃ with 3 hours from room temperature earlier, 600 ℃ of constant temperature 4 hours, again with dropping to room temperature in 2 hours), obtain the negative active core-shell material X VIII that is used for secondary lithium battery of the present invention, the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: the negative active core-shell material that is used for secondary lithium battery and the conductive carbon black that will contain Si-MnO, (molecular structure such as Fig. 2 a) nmp solution do not mix formation slurry (weight ratio after three's oven dry is 85: 5: 10) to the polyamidoimide of complete polymerization at normal temperatures and pressures, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 200 ℃ of following heat treatments 6 hours, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
Embodiment 23 uses the spray drying preparation to contain the negative active core-shell material of silicon/chromium oxide
The preparation method who contains the negative active core-shell material X IX that is used for secondary lithium battery of silicon/chromium oxide is similar to embodiment 18, this negative active core-shell material has " Lantern Festival " structure, active material silicon and chromium oxide are contained in its inside, and the composite particles of conductive black composition, its outside has coated the carbon granule layer from the resin pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, and the weight ratio of its each several part is listed in table 1.
The preparation of the negative pole of Experimental cell: what will contain silicon/chromium oxide is used for secondary lithium battery cathode active material and graphitization mesocarbon bead with 50: 45 ratio mechanical mixture of weight ratio, this mixture and 5% polyamide (molecular structure such as Fig. 2 d) nmp solution are mixed formation slurry (weight ratio that is used for secondary lithium battery cathode active material, graphitization mesocarbon bead and polyamide that contains silicon/chromium oxide is 50: 45: 5) at normal temperatures and pressures, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
Embodiment 24 coats and handles, and adopts TiO 2 Coat the compound particle of siliceous nucleocapsid structure
Prepared siliceous nucleocapsid structure compound particle outermost is coated one deck TiO 2
(1) powder of compound particle is joined (consumption adds the ratio of 10ml metatitanic acid four fourth fat in the 1g compound particle) in the ethanolic solution that contains metatitanic acid four fourth fat, stirred 30 minutes, dropping 30ml contains the aqueous solution of glacial acetic acid, and wherein the aqueous solution and glacial acetic acid volume ratio are 2: 1, mixes and stirs 4 hours.The adding glacial acetic acid promotes the hydrolysis of metatitanic acid four fourth fat on the one hand, can not cause reacting fierce excessively by force because of acidity on the other hand, causes coating inhomogeneous;
(2) solution is filtered, with the powder evaporate to dryness of gained, in wherein heat treatment of inertia, heat treated step is: be raised to 400 ℃ from room temperature in 4 hours, constant temperature 4 hours dropped to room temperature in 2 hours.Obtain the negative active core-shell material that is used for secondary lithium battery of the present invention, this negative active core-shell material outermost layer coats the TiO about 10nm 2
The preparation of the negative pole of Experimental cell: with above-mentioned coating TiO 2Be used for secondary lithium battery cathode active material and carbonaceous mesophase spherules with 60: 30 ratio mechanical mixture of weight ratio, this mixture and 10% polyamide (molecular structure such as Fig. 2 d) nmp solution are mixed formation slurry (weight ratio that is used for secondary lithium battery cathode active material, carbonaceous mesophase spherules and polyamide that contains silicon is 60: 30: 10) at normal temperatures and pressures, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
TiO 2The method that coats is not limited to this, for example can adopt chemical gaseous phase to coat, and coats (ALD) as ald.
Embodiment 25 adopts Al 2 O 3 Coat the compound particle of siliceous nucleocapsid structure
The nucleocapsid structure compound particle outermost that preparation is siliceous coats one deck Al 2O 3:
(1) powder of compound particle is joined (consumption adds the ratio of 20ml 2-aluminium butoxide in the 1g compound particle) in the aqueous isopropanol that contains the 2-aluminium butoxide, stirred 30 minutes, acetylacetone,2,4-pentanedione is a chelating agent, drip deionized water and make its hydrolysis, 2-aluminium butoxide wherein, acetylacetone,2,4-pentanedione and water volume ratio are 25: 1: 2, and regulating the pH value with HCl is 5, mix at 50 ℃ and stir 1 hour;
(2) solution is filtered, with the powder evaporate to dryness of gained, in wherein heat treatment of inertia, heat treated step is: be raised to 300 ℃ from room temperature in 3 hours, constant temperature 4 hours dropped to room temperature in 2 hours.Obtain the secondary lithium battery cathode active material that is used for of the present invention, this negative active core-shell material outermost layer coats the Al about 10 nanometers 2O 3
The preparation of the negative pole of Experimental cell: will be coated with Al 2O 3Be used for secondary lithium battery cathode active material and the nmp solution of 10% polyamide mix at normal temperatures and pressures and form slurry (weight ratio of negative active core-shell material and nylon is 90: 10), evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～20 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
It is pointed out that Al 2O 3Method for coating be not limited to this, as adopting ald (ALD coating).
The subsequent treatment of embodiment 26 pole pieces
In above-mentioned example, after cathode pole piece completes, can adopt atomic deposition (ALD) that pole piece is done corresponding subsequent and coat processing.As shown in Figure 3, this method for coating is coated on above the conductive network inorganic material uniformly, and the controllable thickness of coating makes it can not influence the electronic conductance and the ion transfer of pole piece.
Now coat Al to adopt ald with regard to this method 2O 3Be that an example is elaborated.As shown in Figure 4.The instrument model that system adopts is Savannah-100 (a Shi Jia Science and Technology Ltd.).
Pole piece coats Al 2O 3Concrete steps as follows:
(1) system vacuumizes, and waits for that the reative cell vacuum reaches 10 -2Behind the torr, each part temperatures of heating system, wherein the temperature of reaction cavity is controlled at 250 ℃, and the temperature in trimethyl aluminium source is 150 ℃, and the temperature in aqueous vapor source is 150 ℃;
(2) when the probe temperature of system's each several part reaches target temperature, system is degassed, the gas that adopts that degass is nitrogen, and the purpose of degassing is the steam of removing in the cavity;
(3) place pole piece, open system's lid, close lid after pole piece is put into reative cell, vacuumize;
(4) the reative cell vacuum reaches 10 -1Torr, it is 20sccm that nitrogen flow is set, and opens trimethyl aluminium source and source of water vapor, and the deposition program is set, the deposition program mainly comprises following parameter, the burst length of steam (0.015s can be set), stand-by period (5s), trimethyl aluminium burst length (can establish 0.015s), stand-by period (5s), cycle-index (can be provided with 100 times), the thickness of each cyclic deposition is 0.94A °/cycle, the thickness of deposition is about 10nm;
(5) finish deposition and take out sample;
(6) system degass, shutdown system.The ALD system can design according to the needs of oneself, to satisfy the demand of suitability for industrialized production.
The positive pole preparation of Experimental cell, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1, and charging and discharging curve is seen accompanying drawing 13.
The composition of the negative active core-shell material of table 1 embodiment 1～26 and simulated battery thereof discharge and recharge data
Figure G2010100340081D00311
The C/Si negative active core-shell material (a-1) of embodiment 27 the present invention preparation and the comparative study of existing C/Si negative active core-shell material (b)
Adopt the method described in the embodiment of the invention 2 to prepare C/Si negative active core-shell material (a-1) and negative pole, adopt the method for embodiment 5 among the patent application 200410030990.X to prepare existing C/Si negative active core-shell material (b) and negative pole, be used for comparative study.
Efficient first, charge/discharge capacity and the capability retention of above-mentioned negative active core-shell material studied in use by the simulated battery of composite negative pole and lithium assembling.Simulated battery be metallic lithium foil to electrode, the current density of charge and discharge cycles test is 0.4mA/cm 2, the charging cut-ff voltage is 2V, discharge cut-off voltage is 0.0V.Test result sees Table 2.
As can be drawn from Table 2, the present invention adopts the easily balling-up of C/Si negative active core-shell material (a-1) of the nucleocapsid structure of spray drying technology preparation, and lower specific surface is arranged, and therefore has higher coulombic efficiency first; The more existing negative active core-shell material of negative active core-shell material of the present invention in addition (a-1) (b) has better capability retention.
The Cu/Si negative active core-shell material (a-2) of embodiment 28 the present invention preparation and the comparative study of existing negative active core-shell material (b)
Adopt the method described in the embodiment of the invention 12 to prepare Cu/Si negative active core-shell material (a-2) and negative pole, adopt the method for embodiment 5 among the patent application 200410030990.X to prepare existing negative active core-shell material (b) and negative pole, be used for comparative study.
Battery testing is analogous to embodiment 27, and test structure sees Table 2.
Adopt the Cu/Si negative active core-shell material (a-2) of the nucleocapsid structure of embodiment 12 electronation sedimentations preparation, the Cu layer coats evenly, and concrete pattern is referring to accompanying drawing 12b and accompanying drawing 12c.Evenly the Cu layer that coats helps increasing the conductivity of material, and Cu spreads in the Si particle easily, has firm interface contact between the Cu-Si, the Cu layer also has ductility preferably in addition, even Si particle generation volumetric expansion is pulverized, still contact with the interface that Cu keeps good.Therefore, negative active core-shell material of the present invention (a-2) is compared with existing negative active core-shell material (b), has higher efficient first, better capability retention.
Embodiment 29 adopts the comparative study of amide-type high temperature resistant binder negative pole that is prepared from and the negative pole that adopts the Kynoar adhesive preparation to form
Negative active core-shell material adopts the method for embodiment 1 to prepare.
Electrode 1 adopts the amide-type high temperature resistant binder, and the preparation method is with embodiment 1.
Electrode 2 adopts the Kynoar binding agent, and the each several part proportioning is with the embodiment of the invention 1, and embodiment 5 described methods prepare among preparation method's referenced patent application 200410030990.X.Test structure sees Table 2.
As known from Table 2, adopt the amide-type high temperature resistant binder, play important effect for the material capacity conservation rate, the present invention adopts the amide-type high temperature resistant binder can better improve the cyclical stability of Si negative pole, and the battery that comprises this negative material has higher capacity, enclosed pasture efficient and better capability retention first.
The test result of table 2 embodiment 27-29
Figure G2010100340081D00341
It may be noted that at last the cathode material preparation method that nucleocapsid structure that the present invention proposes is used for the high power capacity of serondary lithium battery is not limited to said method, as adopting Mechanical Method, hydro thermal methods etc. can referenced patent application CN200410030990.X and CN200510082822.X.Inner nuclear material is chosen more than elementary silicon, can also choose Si oxide, and silicon alloy also can select to add the commodity material with carbon element, tin simple substance, tin-oxide and ashbury metal, manganous oxide, one or more in the chromium oxide etc.The amide-type high temperature resistant binder also is not limited to this.

Claims (13)

1. negative material that is used for lithium rechargeable battery, this negative material comprises compound particle, conductive additive and the amide-type high temperature resistant binder with nucleocapsid structure.
2. negative material according to claim 1 is characterized in that, the compound particle of described nucleocapsid structure comprises: the kernel and the outer shell that contains inorganic clad material that contain silica-based active material.
3. negative material according to claim 1 and 2 is characterized in that, described silica-based active material is one or more in silicon, Si oxide, the silicon alloy;
Preferably, described silica-based active material can also be mixed with one or more in material with carbon element, tin simple substance, tin-oxide, ashbury metal, manganous oxide and the chromium oxide.
4. according to each described negative material of claim 1 to 3, it is characterized in that described inorganic clad material is C, Cu, Fe, Ni, Cr, Al 2O 3, TiO 2, Li 2Si 2O 5, Li 2SiO 3, Li 4SiO 4, Li 8SiO 6, SiO 2And Li 3PO 4In one or more.
5. according to each described negative material of claim 1 to 4, it is characterized in that the particle diameter of described kernel is 10 nanometers-4 micron, be preferably 50 nanometers-4 micron, more preferably 500 nanometers-2 micron.
6. according to each described negative material of claim 1 to 5, it is characterized in that described outer shell thickness is 1 nanometer-500 nanometer, be preferably 50 nanometers-100 nanometer, more preferably 50 nanometers-80 nanometer.
7. according to each described negative material of claim 1 to 6, it is characterized in that the particle diameter of the compound particle of described nucleocapsid structure is 100 nanometers～100 micron, is preferably 1 micron～20 microns.
8. according to each described negative material of claim 1 to 7, it is characterized in that described conductive additive is a graphite powder, conductive black, acetylene black, carbon nano-tube, for example Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, carbon fiber, one or more in metal powder and the metallic fiber;
Preferably, the particle diameter of described graphite powder, conductive black, acetylene black or metal powder is 1 nanometer-20 micron;
More preferably, the length of described carbon nano-tube, carbon fiber or metallic fiber is 10 nanometers-20 micron, and diameter is 10 nanometers-500 nanometers.
9. according to each described negative material of claim 1 to 8, it is characterized in that described amide-type high temperature resistant binder is one or more in polyamidoimide, polyamide, the polyimides;
Be preferably in aromatic polyamide acid imide, aromatic polyamide, the aromatic polyimide one or more.
10. according to each described negative material of claim 1 to 9, it is characterized in that the compound particle of described nucleocapsid structure accounts for 3～98wt% of described negative material total weight, is preferably 20～95wt%; Described conductive additive accounts for 1～35wt% of described negative material total weight, is preferably 5-10wt%; Described amide-type high temperature resistant binder accounts for the 1-30wt% of described negative material total weight, is preferably 5-15wt%, more preferably 10wt%.
11. a negative pole that is used for lithium rechargeable battery, described negative pole comprise claim 1 to 10 each described negative material and collector; Preferably, described collector is the carrier of paper tinsel, net, porous body, foams or the corpus fibrosum material of various conductions, for example Copper Foil, nickel screen, nickel foam and carbon felt.
12. the preparation method of the described negative pole of claim 11, this preparation method comprises: with the compound particle of nucleocapsid structure, conductive additive, adhesive coated on collector, in vacuum or inert atmosphere, at 80-450 ℃, be preferably 120 ℃-350 ℃, more preferably heat-treat for 120 ℃-300 ℃, heat treatment time is 10 minutes-10 hours.
13. a lithium rechargeable battery, this secondary cell comprise the described negative pole of claim 11.
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