CN102593446A - Method for preparing active electrode material of lithium ion battery - Google Patents

Method for preparing active electrode material of lithium ion battery Download PDF

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CN102593446A
CN102593446A CN201210042506XA CN201210042506A CN102593446A CN 102593446 A CN102593446 A CN 102593446A CN 201210042506X A CN201210042506X A CN 201210042506XA CN 201210042506 A CN201210042506 A CN 201210042506A CN 102593446 A CN102593446 A CN 102593446A
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lithium ion
ion battery
electrode material
active electrode
nanocrystal
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魏飞
贾希来
卢云峰
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Tsinghua University
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Abstract

The invention discloses a method for preparing an active electrode material of a lithium ion battery. The method comprises the following steps of: preparing a nano-crystal with electrochemical activity into an aqueous solution, and adding a carbon source and a surface active agent into the aqueous solution to form a uniform and stable mixture solution; and preparing the mixture solution into spherical particles under the condition that the temperature is between 200 and 900 DEG C through a spray granulation method, and performing heat treatment on the spherical particles in 400-900 DEG nitrogen gas so as to form the active electrode material of the lithium ion battery. Conductive networks are distributed in the active electrode material, and the active electrode material has a porous structure, so that the active electrode material has good lithium ion and electron transmission channels; and the lithium ion battery prepared from the active electrode material has high specific capacity, high-current charging and discharging and high cyclical stability. The method for preparing the electrode material of the lithium ion battery through a spraying method can be easily applied to mass production, and is generally used for preparing various high-performance electrode materials of the lithium ion battery.

Description

A kind of preparation method of lithium ion battery active electrode material
Technical field
The present invention relates to a kind of preparation method of lithium ion battery active electrode material, belong to Chemical Engineering and derived energy chemical field.
Background technology
Along with the mankind to the aggravation of energy demand and becoming increasingly conspicuous of environmental problem, lithium ion battery has application market widely.The lithium ion battery structure mainly is made up of electrode, barrier film and electrolyte.Wherein, the raising of its electrode active material performance is depended in the development of lithium ion battery to a great extent.At present, lithium ion battery mobile phone and notebook computer etc. many aspect extensive application, but lithium ion battery expanded to aspects such as power vehicle and hybrid vehicle run into an important difficult problem, its energy density is badly in need of further raising with power density.
The negative active core-shell material of lithium ion battery is main with graphite, reach more than 52% of occupation rate of market, but its capacity is lower.Therefore people have developed following several types of negative active core-shell materials: silicon class negative active core-shell material, its theoretical capacity are at 4200mAh/g, but the extremely difficult control of its stability.Use the method for chemical vapor deposition, can accomplish more stable silicon nanowires negative active core-shell material, but on the cost of commercial application, still be difficult to promote (C.K.Chan, et al, Nat Nano, 2008,3,31-35.).Tin class alloy can reach the capacity of 800～900mAh/g, but its high-rate charge-discharge capability is never broken through at present.And there be very big safety and stable problem in metal lithium sheet as negative active core-shell material.Metal oxide is like Fe 3O 4, Fe 2O 3, SnO 2Deng, have very high theoretical capacity as new negative active core-shell material.Simultaneously, because material itself is nontoxic, cheapness, and abundant raw material and receiving much concern.But the metal oxide negative active core-shell material embeds and deviates from the process of active material at lithium ion and also has huge volumetric expansion, and this causes the quick loss of its chemical property.
On the other hand, nearly all anode active material of lithium ion battery is (like LiCoO 2, LiMn 2O 4, LiNi 0.5Mn 1.5O 4, LiFePO 4, LiMnPO 4, Li 3V 2(PO 4) 3) the fast charging and discharging ability all very poor, this has much relations with the poorly conductive of positive electrode active materials self.For the high rate during charging-discharging that improves positive electrode active materials and lithium ion battery negative active material design class seemingly, a large amount of work is carried out around following two aspects: the electric conductivity and the size that reduces positive electrode active materials that improve positive electrode active materials.In order to improve the conductivity performance, the method for positive electrode active materials being carried out various carbon coatings is general thinkings, can improve the reversible capacity of anode active material of lithium ion battery to a certain extent, but high rate performance and stable circulation performance is still restricted.
Recently, the method that coats based on SWCN network and graphene nanometer sheet has had large increase (C.Ban, et al, Adv.Mater., 2010,22, E145-E149 to the electrode high rate performance of lithium ion battery; G.Zhou, et al, Chem.Mater., 2010,22,5306-5313.), but its preparation process also has considerable restraint apart from commercial application.In addition, utilize the nano material preparation technology to reduce the crystallite dimension of lithium ion cell electrode active material, can reduce the diffusion length of lithium ion in the active material the inside.But this is to the tap density and the energy density deleterious impact of electrode material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lithium ion battery active electrode material; This method is through carrying out the structural design of three dimension scale to existing lithium ion battery electrode material; Realize that with easy mist projection granulating method and further heat treatment the material with carbon element of conduction interts in the entire electrode active material; With the high rate during charging-discharging and long useful life of realizing lithium ion battery, thereby improve the performance of present lithium ion battery effectively.
Technical scheme of the present invention is following:
A kind of preparation method of lithium ion battery active electrode material is characterized in that this preparation method comprises following steps:
1) adopt the method for hydro-thermal or co-precipitation, the nanocrystal of preparation lithium ion battery electrode material is mixed with the quality percentage composition at 0.1～20% the aqueous solution with resulting nanocrystal;
2) in the said aqueous solution, adding the quality percentage composition is 0.05～10% carbon source, and the quality percentage composition is 0.05～10% surfactant, forms uniform and stable mixture solution;
3), make mixture solution under 200～900 ℃ temperature conditions, form spherical particle through the method for mist projection granulating;
4), form the lithium ion battery active electrode material with the heat treatment in 400～900 ℃ nitrogen of gained spheric granules.
In the technique scheme, the nanocrystal of described lithium ion battery electrode material comprises lithium ion battery negative material nanocrystal and anode material for lithium-ion batteries nanocrystal, and described lithium ion battery negative material nanocrystal is Fe 3O 4, Fe 2O 3, SnO 2, TiO 2, Li 4Ti 5O 12With among the Si one or more; Described anode material for lithium-ion batteries nanocrystal is LiCoO 2,, LiMn 2O 4, LiFePO 4, LiMnPO 4, Li 3V 2(PO 4) 3And LiNi 0.5Mn 1.5O 4In one or several.The granularity of the nanocrystal of described lithium ion battery electrode material is 2～100 nanometers.The carbon source that is added is one or more in sucrose, glucose, graphite, conductive black, CNT and the Graphene.The surfactant that is added is polyvinyl alcohol, block copolymer P123, block copolymer F127, polyoxyethylene or polyvinylpyrrolidone.
Mist projection granulating method of the present invention adopts thermal spray or gasification spraying.Prepared lithium ion battery active electrode material is the spheric granules of 200 nanometers～10 micron, has 10～60% porosity.
Present technique has following advantage: 1. technical process is simple, and commercial plant is large-scale application, easy production in batch; 2. the method for mist projection granulating can improve the tap density of lithium ion cell electrode active material, thereby improves its energy density; 3. in resulting electrode active material, there is the passage of porous, is convenient to the transmission of electrolyte, thereby realize high rate during charging-discharging; 4. in resulting electrode active material, there is carbonaceous conductive network, is convenient to the conduction of electronics, thereby realize high rate during charging-discharging through electrode active material; 5. as universal method, the preparation technology of this lithium ion cell electrode active material can be generalized in the preparation of nearly all lithium ion battery negative active material and positive electrode active materials.
Description of drawings
Fig. 1. be gasification sprayer unit and process chart.
Wherein: the 1-mixture solution; The 2-carrier gas; The 3-sprayer; The 4-dry section; The 5-thermal treatment zone; 6-product collecting region; 7-tail gas.
Fig. 2. the Fe that carbon coats 3O 4The shape appearance figure of negative material.
Fig. 3. the Fe that carbon coats 3O 4The multiplying power of negative material and stable circulation performance.
Fig. 4. the Fe that CNT interts 3O 4The shape appearance figure of negative material.
Fig. 5. the Fe that CNT interts 3O 4The multiplying power of negative material and stability.
Fig. 6. the Li that CNT interts 3V 2(PO 4) 3The shape appearance figure of positive electrode.
Fig. 7. the Li that CNT interts 3V 2(PO 4) 3The multiplying power of positive electrode and stability, wherein the current density of 1C is 133.4mAg -1
Embodiment
Fig. 1 is the gasification sprayer unit and the process chart of lithium ion battery electrode material among the present invention, and this device mainly comprises the sprayer 3 of mixture solution atomizing, the drop that atomizes is become the solid granulates thermal treatment zone 5 and product collecting region.In conjunction with Fig. 1 its concrete preparation process is described.
The nanocrystal that at first prepares various lithium ion battery electrode materials with methods such as co-precipitation, hydro-thermals.For example with Fe 3O 4Being example, is 2: 1 FeCl with mol ratio 3And FeCl 24H 2O adds in the aqueous solution, and adding ammoniacal liquor can go out Fe through prepared by co-precipitation 3O 4Nanocrystal, the aqueous solution of preparing the quality percentage composition then and be 0.1～20% nanocrystal is subsequent use.In above-mentioned solution, add a certain amount of carbon source and surfactant, be dispersed into uniform mixture solution.Carbon source is at least a in sucrose, glucose, conductive black, graphite, CNT or the Graphene here; Surfactant is a kind of in polyvinyl alcohol, block copolymer P123, block copolymer F127, polyoxyethylene and the polyvinylpyrrolidone.In the final mixture solution, the quality percentage composition of carbon source is 0.05～10%, and the quality percentage composition of surfactant is 0.05～10%.With the mixture solution for preparing gasify the spraying or thermal spray, the condition of mist projection granulating is 200～900 ℃, used carrier gas is a nitrogen.Like accompanying drawing 1, mixture solution forms droplet through the atomizing of air-flow, and the droplet of these atomizings forms pressed powder through the drying of the thermal treatment zone, and collects corresponding product at the afterbody of gasification sprayer unit.With further heat treatment in 400-900 ℃ nitrogen of the pressed powder of collecting, obtain final lithium ion cell electrode active material.The carbon source that is added in the lithium ion cell electrode active material that this process obtains can form the surface that continuous carbon network packet overlays on nanocrystal; Perhaps be interspersed in the entire electrode active material; Improve the electric conductivity of electrode material; And in the carbon network, can further intert CNT, graphite or Graphene.Final lithium ion battery electrode material is prepared into the negative pole or the positive pole of lithium ion battery, and carries out electro-chemical test.
The nanocrystal of described lithium ion battery electrode material comprises lithium ion battery negative material nanocrystal and anode material for lithium-ion batteries nanocrystal, and described lithium ion battery negative material nanocrystal is Fe 3O 4, Fe 2O 3, SnO 2, TiO 2, Li 4Ti 5O 12With among the Si one or more; Described anode material for lithium-ion batteries nanocrystal is LiCoO 2,, LiMn 2O 4, LiFePO 4, LiMnPO 4, Li 3V 2(PO 4) 3And LiNi 0.5Mn 1.5O 4In one or several.The granularity of the nanocrystal of described lithium ion battery electrode material is 2～100 nanometers.The carbon source that is added is one or more in sucrose, glucose, graphite, conductive black, CNT and the Graphene.The surfactant that is added is polyvinyl alcohol, block copolymer P123, block copolymer F127, polyoxyethylene or polyvinylpyrrolidone.
Mist projection granulating method of the present invention adopts thermal spray or gasification spraying.Prepared lithium ion battery active electrode material is the spheric granules of 200 nanometers～10 micron, has 10～60% porosity.
To come the preparation method of lithium ion battery active electrode material provided by the invention is made further description by 16 instantiations below.
Embodiment 1
At H 2In the O solution, the adding mol ratio is 2: 1 FeCl 3And FeCl 24H 2O stirs, and adds 28% ammoniacal liquor fast, obtains the Fe of 3～12nm size behind the reaction 30min 3O 4Nanocrystal, preparation quality percentage composition are 1.0% Fe 3O 4The aqueous solution.With adding the sucrose of quality percentage composition 2.0% and 2.0% polyvinyl alcohol in the above-mentioned solution, formation mixed liquor solution stirs.Said mixture solution is carried out mist projection granulating with the gasification sprayer unit, and temperature is 450 ℃, obtains spheric granules, with these spheric granules further 600 ℃ of annealing in process in nitrogen, thereby obtains carbon/Fe 3O 4Negative material.The electron scanning micrograph of accompanying drawing 2 shows, these Fe 3O 4Nanocrystal is assembled in the continuous poriferous carbon skeleton, forms the spheric granules of micron size.With this carbon/Fe 3O 4Negative material is made the negative pole of lithium ion battery, and carries out electrochemical property test.Accompanying drawing 3 is multiplying power and stabilities of this negative pole.The result shows, the carbon/Fe of method for preparing 3O 4The negative material high rate performance is extremely excellent.At 156mA g -1Constant current under, this negative material has about 1000mAh g -1Reversible capacity; At big electric current 4690mA g -1Down, this negative material can perhaps discharge with interior completion charging at 10 minutes, and its capacity remains on 580mAh g -1This negative material is extremely stable, almost not decay in circulation.Simultaneously, the unit are specific capacity of this negative material reaches 1.5mAhcm -2, very near the level of commercial application.
Embodiment 2
At H 2In the O solution, the adding mol ratio is 2: 1 FeCl 3And FeCl 24H 2O stirs, and adds 28% ammoniacal liquor fast, reacts the Fe that obtains 3～12nm size after 30 minutes 3O 4Nanocrystal, preparation quality percentage composition are 0.6% Fe 3O 4The aqueous solution.Above-mentioned solution is added the sucrose of quality percentage composition 0.1%, the native graphite of 0.2% dispersion and 3.0% block copolymer F127, stirring forms uniform mixture solution.Said mixture solution is carried out mist projection granulating with the gasification sprayer unit, and temperature is 400 ℃, obtains spheric granules.With these spheric granules further 600 ℃ of annealing in process in nitrogen, thereby obtain the Fe that the graphite of porous coats 3O 4Negative active core-shell material.Fe with this graphite coating 3O 4Negative material is made the negative pole of lithium ion battery, and carries out electro-chemical test.
Embodiment 3
At H 2In the O solution, the adding mol ratio is 2: 1 FeCl 3And FeCl 24H 2O stirs, and adds 28% ammoniacal liquor fast, reacts the Fe that obtains 3～12nm size after 30 minutes 3O 4Nanocrystal, preparation quality percentage composition are 2.0% Fe 3O 4The aqueous solution.Above-mentioned solution is added the sucrose of quality percentage composition 1.0%, 0.1% CNT and 0.5% block copolymer P123, stirring forms uniform mixture solution.Said mixture solution is carried out mist projection granulating with the gasification sprayer unit, and temperature is 500 ℃, obtains spheric granules.With these spheric granules further 560 ℃ of annealing in process in nitrogen, thereby obtain the Fe that the CNT of porous interts 3O 4Negative active core-shell material.The electron scanning micrograph of accompanying drawing 4 shows that these negative active core-shell materials are form of spherical particles, and is interting carbon nano-tube fibre.The Fe that the CNT that obtains is interspersed 3O 4Negative active core-shell material is made the negative pole of lithium ion battery, and carries out electro-chemical test.Accompanying drawing 5 shows that high rate performance and the cycle performance of this negative material is very excellent.
Embodiment 4
At H 2In the O solution, the adding mol ratio is 2: 1 FeCl 3And FeCl 24H 2O stirs, and adds 28% ammoniacal liquor fast, reacts the Fe that obtains 3～12nm size after 30 minutes 3O 4Nanocrystal, preparation quality percentage composition are 4.0% Fe 3O 4The aqueous solution.The glucose that adds quality percentage composition 2.0% then, 0.2% carbon black, 0.6% graphite and 4.0% polyoxyethylene are mixed the uniform mixture solution of even formation.Said mixture solution is carried out mist projection granulating with the thermal spray device, and temperature is 250 ℃, obtains spheric granules.With these spheric granules further 600 ℃ of annealing in process in nitrogen, obtain the Fe of the lamella graphite coating of porous 3O 4Negative active core-shell material.The Fe that the graphite that thermal spray is obtained coats 3O 4Negative material is made the negative pole of lithium battery, and carries out electro-chemical test.
Embodiment 5
In JJ-2 type histocyte refiner, add FeCl 3In H 2Among the O, make target product Fe 2O 3The quality percentage composition be 1.2%, add a certain amount of 28% ammoniacal liquor, high-speed stirred 2 hours.With the sucrose that adds quality percentage composition 0.2% in the above-mentioned solution, 0.1% graphite oxide, 0.06% CNT and 2% polyvinylpyrrolidone, high-speed stirred evenly forms mixture solution.Said mixture solution is carried out mist projection granulating with the heat of gasification sprayer unit, and temperature is 450 ℃, obtains spheric granules.Then resulting granules is handled at 560 ℃ AN, obtained the interspersed Fe of Graphene coated carbon nanotube of porous 2O 3Negative active core-shell material.The Fe that the Graphene coated carbon nanotube that obtains is interspersed 2O 3Negative active core-shell material is made the negative pole of lithium ion battery, and carries out electro-chemical test.
Embodiment 6
At H 2In the O solution, add SnCl 45H 2O, NaH 2PO 4And Na 2SO 4,, obtain the SnO about 5nm in 180 ℃ of hydro-thermal reactions 24 hours 2Nanocrystal.The configuration quality percentage composition is 1% SnO 2The aqueous solution of nanocrystal, and then to the sucrose that wherein adds quality percentage composition 0.8%, 0.06% graphite oxide; 0.05% CNT; And 1.5% block copolymer P123, stirring forms uniform mixture solution, and said mixture solution is carried out mist projection granulating with the gasification sprayer unit; Temperature is 450 ℃, obtains the interspersed SnO of CNT of lamella graphite oxide parcel 2Spheric granules.And then with of the AN processing of these spheric granules, thereby obtain the SnO that the Graphene coated carbon nanotube is interted at 450 ℃ 2Negative active core-shell material.The SnO that this Graphene coated carbon nanotube is interspersed 2Negative active core-shell material is made the negative pole of lithium ion battery, and carries out electro-chemical test.
Embodiment 7
In toluene solvant, add titanium propanolate and oleic acid, and then add the aqueous solution of the tert-butylamine that contains, stir, transfer in the agitated reactor, 180 ℃ of following hydro-thermal reactions 12 hours obtain the TiO of 2～5nm 2Nanocrystal.The TiO of configuration quality percentage composition 1% 2The aqueous solution of nanocrystal, the sucrose of adding 0.4%, 0.1% CNT and 1% polyoxyethylene form uniform mixture solution.With the spraying of gasifying of this mixture solution, vapo(u)rizing temperature is 400 ℃, obtains powdery granule, with the 400 ℃ of annealing down in nitrogen of resulting powdery granule, obtains the TiO that CNT interts 2Negative active core-shell material.The TiO that this CNT is interspersed 2Negative active core-shell material is made the negative pole of lithium ion battery, and carries out electro-chemical test.
Embodiment 8
In volume ratio 1: 1 H 2O/C 2H 5In the OH mixed solution, the adding mol ratio is 4: 5 LiOHH 2O and Ti (OC 4H 9) 4) as precursor, make target product Li 4Ti 5O 12Mass content 12%, stir, and then add 5% sucrose, 0.8% CNT, 1% activated carbon black and 1% polyvinylpyrrolidone form uniform mixture solution.This mixture solution is carried out thermal spray, and vapo(u)rizing temperature is 250 ℃, obtains Powdered spheric granules.With the particle that obtains further at 800 ℃ AN, thereby obtain the Li that CNT interts 4Ti 5O 12Negative active core-shell material.The Li that this CNT is interspersed 4Ti 5O 12Negative active core-shell material is made the negative pole of lithium ion battery, and carries out electro-chemical test.
Embodiment 9
At H 2(Si nanocrystal size is 50～100nm) to add the quality percentage composition in the O solvent and be 0.1% commercial Si powder; Be uniformly dispersed; Add 0.5% sucrose again to above-mentioned solution, 0.5% graphite and 0.6% block copolymer P123, the formation mixture solution stirs.Said mixture solution is carried out mist projection granulating with the gasification sprayer unit, and temperature is 900 ℃, obtains powdery granule.This particle is further handled at 900 ℃ AN, thereby obtained the porous Si negative active core-shell material that lamella graphite wraps up.The Si negative active core-shell material of the graphite parcel that obtains is made the negative pole of lithium ion battery, and carry out electro-chemical test.
Embodiment 10
At H 2(Si nanocrystal size is 50～100nm) and 0.4% Fe to add the commercial Si powder that the quality percentage composition is 0.6wt% in the O solvent 3O 4(size is 3～12nm) to nanocrystal, is uniformly dispersed, and adds 0.1% sucrose again to above-mentioned solution, and 0.8% graphite and 0.5% block copolymer P123 form uniform mixed liquor solution.Said mixture solution is carried out mist projection granulating with the gasification sprayer unit, and temperature is 500 ℃, obtains powdery granule.This particle is further handled at 600 ℃ AN, obtained the porous Si/Fe of lamella graphite parcel 3O 4Negative active core-shell material.Porous Si/Fe with the graphite parcel that obtains 3O 4Negative active core-shell material is made the negative pole of lithium ion battery, and carries out electro-chemical test.
Embodiment 11
At H 2In the O solution, add V by the metering ratio 2O 5, NH 4H 2PO 4, Li 2CO 3And oxalic acid, make Li 3V 2(PO 4) 3Quality percentage composition corresponding in the aqueous solution is 1.5%; After stirring, prepare uniform solution, and then add the CNT of quality percentage composition 0.05%, 0.05% carbon black; 0.5% sucrose and 1% block copolymer P123 form uniform mixture solution.With the spraying of gasifying of this mixture solution, vapo(u)rizing temperature is 450 ℃, obtains the Li that CNT interts 3V 2(PO 4) 3The spheric granules of precursor.With the further 800 ℃ of annealing in nitrogen of this precursor spheric granules, can obtain the Li that CNT interts 3V 2(PO 4) 3The positive electrode active materials particle, its pattern is shown in the electron micrograph among Fig. 6.It is made the positive pole of lithium ion battery, and carry out electro-chemical test, accompanying drawing 7 shows the Li under this structure 3V 2(PO 4) 3Chemical property is extremely excellent.
Embodiment 12
At H 2In the O solution, the adding mol ratio is 1: 1 MnO 2And LiOHH 2O stirs, and then above-mentioned suspension-turbid liquid is transferred in the agitated reactor, under 180 ℃ airtight high pressure, carries out hydro-thermal reaction 4 days, obtains the LiMn of 20～50nm size 2O 4Nanocrystal.The configuration quality percentage composition is 2% LiMn 2O 4The aqueous solution of nanocrystal, in solution, add the sucrose of quality percentage composition 0.1% again, 0.5% CNT and 1.0% block copolymer P123, the formation mixture solution stirs.Said mixture solution is carried out mist projection granulating with the gasification sprayer unit, and temperature is 450 ℃, obtains powdery granule.With the particle that obtains 400 ℃ of further heat treatments, thereby obtain the LiMn that CNT interts 2O 4Positive electrode active materials.The LiMn that the CNT that obtains is interspersed 2O 4Positive electrode active materials is made the positive pole of lithium ion battery, and carries out electro-chemical test.
Embodiment 13
In volume ratio 1: 2 H 2O/H 2O 2In the mixed solution, 1: 4 in molar ratio adding CoCl 26H 2O and LiOHH 2O, stirring forms stable solution, above-mentioned solution is transferred in the agitated reactor reacted 24 hours down at 200 ℃ then, obtains LiCoO 2Nanocrystal.It is 10.0% LiCoO that configuration contains the quality percentage composition 2The aqueous solution of nanocrystal, again to the sucrose that wherein adds 1%, 0.8% activated carbon black, 0.8% CNT and 2.0% polyoxyethylene form uniform mixture solution.This mixture solution is carried out thermal spray, and vapo(u)rizing temperature is 200 ℃, obtains the LiCoO that CNT interts 2Spheric granules.With this spheric granules further in nitrogen 800 ℃ of annealing obtain the LiCoO that CNT interts 2Positive electrode active materials.Then it is made the positive pole of lithium ion battery, and carry out electro-chemical test.
Embodiment 14
Be 1: 1: 1 adding Li in molar ratio 2CO 3, Mn (NO 3) 2And NH 4H 2PO 4To H 2In the O solution, stirring forms stable solution, then above-mentioned solution is transferred in the agitated reactor, reacts 24 hours down at 200 ℃, obtains LiMnPO 4Nanocrystal.Configuration contains 1% LiMnPO 4The solution of nanocrystal, again to the sucrose that wherein adds 0.6%, 0.1% graphite oxide and 0.6% polyvinylpyrrolidone form uniform suspension-turbid liquid.With the spraying of gasifying of this suspension-turbid liquid, vapo(u)rizing temperature is 450 ℃, obtains the LiMnPO that CNT interts 4Spheric granules.The further annealing of this spheric granules is obtained positive electrode active materials, make the positive pole of lithium battery then, and carry out electro-chemical test.
Embodiment 15
Be added with micro-H 2O 2The aqueous solution in, be to add Fe (NO at 1: 1 in molar ratio 3) 39H 2O and NH 4H 2PO 4, through adding the LiOHH of same mol ratio after the vigorous stirring again 2O makes final LiFePO 4Content in solution is 2%, continues to add 0.05% CNT, 0.1% activated carbon black, 0.5% glucose and 1% block copolymer P123 then, forms uniform mixture solution.With the spraying of gasifying of this mixture solution, vapo(u)rizing temperature is 450 ℃, obtains the LiFePO that CNT interts 4The powdery granule of the precursor of positive electrode.With the further annealing in 800 ℃ of nitrogen of this particle, obtain the LiFePO that CNT interts 4Positive electrode active materials.The LiFePO that this CNT is interspersed 4Positive electrode active materials is made the positive pole of lithium ion battery, and carries out electro-chemical test.
Embodiment 16
At H 2In the O solution, add LiCH by the metering ratio 3COO2H 2O, Ni (CH 3COO) 24H 2O and Mn (CH 3COO) 24H 2O, the target product LiNi that makes generation 0.5Mn 1.5O 4The quality percentage composition of the corresponding whole aqueous solution is 12%, adds 0.5% CNT then, 0.5% activated carbon black, and 1% sucrose and 2% polyoxyethylene form uniform mixture solution.This mixture solution is carried out thermal spray, and vapo(u)rizing temperature is 200 ℃, obtains powdery granule.With the further 750 ℃ of annealing in process in nitrogen of the powdery granule that obtains, obtain the LiNi that CNT interts 0.5Mn 1.5O 4Positive electrode active materials.Then that the CNT of gained is interspersed LiNi 0.5Mn 1.5O 4Positive electrode active materials is made the positive pole of lithium ion battery, and carries out electro-chemical test.
The embodiment tabulation:
Figure BDA0000137538610000081
Figure BDA0000137538610000091

Claims (7)

1. the preparation method of a lithium ion battery active electrode material is characterized in that this preparation method comprises following steps:
1) adopt the method for hydro-thermal or co-precipitation, the nanocrystal of preparation lithium ion battery electrode material is mixed with the quality percentage composition at 0.1～20% the aqueous solution with resulting nanocrystal;
2) in the said aqueous solution, adding the quality percentage composition is 0.05～10% carbon source, and the quality percentage composition is 0.05～10% surfactant, forms uniform and stable mixture solution;
3), make mixture solution under 200～900 ℃ temperature conditions, form spherical particle through the method for mist projection granulating;
4), form the lithium ion battery active electrode material with the heat treatment in 400～900 ℃ nitrogen of gained spheric granules.
2. according to the preparation method of the described a kind of lithium ion battery active electrode material of claim 1; It is characterized in that: the nanocrystal of described lithium ion battery electrode material comprises lithium ion battery negative material nanocrystal and anode material for lithium-ion batteries nanocrystal, and described lithium ion battery negative material nanocrystal is Fe 3O 4, Fe 2O 3, SnO 2, TiO 2, Li 4Ti 5O 12With among the Si one or more; Described anode material for lithium-ion batteries nanocrystal is LiCoO 2,, LiMn 2O 4, LiFePO 4, LiMnPO 4, Li 3V 2(PO 4) 3And LiNi 0.5Mn 1.5O 4In one or several.
3. according to the preparation method of claim 1 or 2 described a kind of lithium ion battery active electrode materials, it is characterized in that: the granularity of the nanocrystal of described lithium ion battery electrode material is 2～100 nanometers.
4. according to the preparation method of the described a kind of lithium ion battery active electrode material of claim 1, it is characterized in that: the carbon source that is added is one or more in sucrose, glucose, graphite, conductive black, CNT and the Graphene.
5. according to the preparation method of the described a kind of lithium ion battery active electrode material of claim 1, it is characterized in that: the surfactant that is added is polyvinyl alcohol, block copolymer P123, block copolymer F127, polyoxyethylene or polyvinylpyrrolidone.
6. according to the preparation method of the described a kind of lithium ion battery active electrode material of claim 1, it is characterized in that: described mist projection granulating method adopts thermal spray or gasification spraying.
7. according to the preparation method of the described a kind of lithium ion battery active electrode material of claim 1, it is characterized in that: prepared lithium ion battery active electrode material is the spheric granules of 200 nanometers～10 micron, has 10～60% porosity.
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CN103022463A (en) * 2012-12-20 2013-04-03 中国东方电气集团有限公司 Manganese-based compound cathode material of lithium battery and preparation method of material
CN103035899A (en) * 2013-01-14 2013-04-10 山东天润丰新能源科技有限公司 Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer
CN103151509A (en) * 2013-03-18 2013-06-12 江苏悦达墨特瑞新材料科技有限公司 Lithium titanate-graphene nano composite electrode material and preparation method thereof
CN103413927A (en) * 2013-08-12 2013-11-27 浙江大学 Lithium titanate/iron sesquioxide composite lithium ion battery cathode material and preparation method thereof
CN103500822A (en) * 2013-10-10 2014-01-08 暴宁钟 Preparation method of carbon-modified nano Li4Ti5O12-porous graphene composite electrode material
CN103887509A (en) * 2014-03-24 2014-06-25 佛山市德方纳米科技有限公司 Lithium iron phosphate-based composite conductor positive electrode material and preparation method thereof as well as positive electrode and lithium battery
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CN104852033A (en) * 2015-04-01 2015-08-19 北京交通大学 Preparation method for three-dimensional composite lithium titanate negative material
CN105529449A (en) * 2016-01-29 2016-04-27 珠海银隆新能源有限公司 Lithium titanate electrode material and preparation method thereof
CN105552370A (en) * 2016-02-24 2016-05-04 苏州太阳源纳米科技有限公司 Spherical cathode material for lithium-ion secondary battery and preparation method of spherical cathode material
CN105702925A (en) * 2016-01-29 2016-06-22 珠海银隆新能源有限公司 Lithium titanate electrode material and preparation method therefor
CN105762345A (en) * 2016-04-29 2016-07-13 湖北金泉新材料有限责任公司 Composite cathode material and preparation method thereof and lithium ion battery
CN106276910A (en) * 2015-08-27 2017-01-04 东莞市翔丰华电池材料有限公司 A kind of lithium ion battery low temperature graphite cathode material preparation method
US20170214052A1 (en) * 2016-01-25 2017-07-27 Ford Cheer International Limited Electrode having nanocrystal assembled active clusters embodied in conductive network structures, and battery having same, and fabrication method of same
CN107026266A (en) * 2017-06-05 2017-08-08 深圳职业技术学院 A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole materials
CN107706372A (en) * 2017-09-12 2018-02-16 山东大学 A kind of combination electrode material of Mxene claddings and preparation method thereof
CN108336332A (en) * 2018-01-22 2018-07-27 山西大学 A kind of tin dioxide powder and preparation method thereof
CN108910940A (en) * 2018-07-16 2018-11-30 杭州电子科技大学 A kind of online cracking atomization composite precursor preparation SnO2The method of/amorphous carbon nano-composite material
WO2019019407A1 (en) * 2017-07-26 2019-01-31 中能中科（天津）新能源科技有限公司 Lithium-containing electrode, preparation method therefor and lithium battery containing same
CN110061234A (en) * 2019-05-27 2019-07-26 河南科技学院 A kind of anode material for lithium-ion batteries and preparation method thereof
CN111554868A (en) * 2020-04-07 2020-08-18 湖南大学 Power battery material with core-shell structure and preparation method thereof
CN112186167A (en) * 2020-10-28 2021-01-05 陕西彩虹新材料有限公司 Preparation method of template-method-coated high-nickel ternary cathode material for lithium ion battery
CN112467127A (en) * 2020-09-24 2021-03-09 陕西红马科技有限公司 Coating modified lithium ion ternary cathode material and preparation method thereof
CN113871209A (en) * 2021-08-30 2021-12-31 兰州大学 Carbon-coated graphene-iron oxide composite electrode material and preparation method and application thereof
CN114368787A (en) * 2022-01-10 2022-04-19 东华大学 High-conductivity and high-stability lithium manganate material and application thereof

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CN103022463A (en) * 2012-12-20 2013-04-03 中国东方电气集团有限公司 Manganese-based compound cathode material of lithium battery and preparation method of material
CN103035899A (en) * 2013-01-14 2013-04-10 山东天润丰新能源科技有限公司 Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer
CN103035899B (en) * 2013-01-14 2015-05-27 山东天润丰新能源科技有限公司 Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer
CN103151509B (en) * 2013-03-18 2015-04-22 江苏悦达墨特瑞新材料科技有限公司 Lithium titanate-graphene nano composite electrode material and preparation method thereof
CN103151509A (en) * 2013-03-18 2013-06-12 江苏悦达墨特瑞新材料科技有限公司 Lithium titanate-graphene nano composite electrode material and preparation method thereof
CN103413927A (en) * 2013-08-12 2013-11-27 浙江大学 Lithium titanate/iron sesquioxide composite lithium ion battery cathode material and preparation method thereof
CN103413927B (en) * 2013-08-12 2015-04-29 浙江大学 Lithium titanate/iron sesquioxide composite lithium ion battery cathode material and preparation method thereof
CN103500822A (en) * 2013-10-10 2014-01-08 暴宁钟 Preparation method of carbon-modified nano Li4Ti5O12-porous graphene composite electrode material
CN103500822B (en) * 2013-10-10 2015-07-15 暴宁钟 Preparation method of carbon-modified nano Li4Ti5O12-porous graphene composite electrode material
CN103887509A (en) * 2014-03-24 2014-06-25 佛山市德方纳米科技有限公司 Lithium iron phosphate-based composite conductor positive electrode material and preparation method thereof as well as positive electrode and lithium battery
CN103887509B (en) * 2014-03-24 2016-07-06 佛山市德方纳米科技有限公司 Iron phosphate lithium-based composite conductor positive electrode and preparation method, positive pole and lithium battery
CN104300120A (en) * 2014-09-17 2015-01-21 山东精工电子科技有限公司 Hydrothermal synthesis method of nano-lithium titanate material
CN104852033A (en) * 2015-04-01 2015-08-19 北京交通大学 Preparation method for three-dimensional composite lithium titanate negative material
CN104852033B (en) * 2015-04-01 2017-06-23 北京交通大学 A kind of preparation method of three-dimensional composite lithium titanate negative material
CN106276910B (en) * 2015-08-27 2019-09-10 福建翔丰华新能源材料有限公司 A kind of lithium ion battery low temperature graphite cathode material preparation method
CN106276910A (en) * 2015-08-27 2017-01-04 东莞市翔丰华电池材料有限公司 A kind of lithium ion battery low temperature graphite cathode material preparation method
WO2017132045A1 (en) * 2016-01-25 2017-08-03 Ford Cheer International Limited Electrode having nanocrystal assembled active clusters embodied in conductive network structures, and battery having same, and fabrication method of same
US20170214052A1 (en) * 2016-01-25 2017-07-27 Ford Cheer International Limited Electrode having nanocrystal assembled active clusters embodied in conductive network structures, and battery having same, and fabrication method of same
EP3408881A4 (en) * 2016-01-25 2019-07-17 Ford Cheer International Limited Electrode having nanocrystal assembled active clusters embodied in conductive network structures, and battery having same, and fabrication method of same
CN109075319A (en) * 2016-01-25 2018-12-21 丰捷国际有限公司 The electrode of ergophore with the nanocrystal assembly implemented in conductive mesh structure, and the manufacturing method with the battery pack of the electrode and the electrode
CN105529449A (en) * 2016-01-29 2016-04-27 珠海银隆新能源有限公司 Lithium titanate electrode material and preparation method thereof
CN105702925A (en) * 2016-01-29 2016-06-22 珠海银隆新能源有限公司 Lithium titanate electrode material and preparation method therefor
CN105552370A (en) * 2016-02-24 2016-05-04 苏州太阳源纳米科技有限公司 Spherical cathode material for lithium-ion secondary battery and preparation method of spherical cathode material
CN105762345A (en) * 2016-04-29 2016-07-13 湖北金泉新材料有限责任公司 Composite cathode material and preparation method thereof and lithium ion battery
CN105762345B (en) * 2016-04-29 2019-03-29 湖北金泉新材料有限责任公司 A kind of composite positive pole, preparation method and lithium ion battery
CN107026266B (en) * 2017-06-05 2019-04-09 深圳职业技术学院 A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material
CN107026266A (en) * 2017-06-05 2017-08-08 深圳职业技术学院 A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole materials
WO2019019407A1 (en) * 2017-07-26 2019-01-31 中能中科（天津）新能源科技有限公司 Lithium-containing electrode, preparation method therefor and lithium battery containing same
CN107706372B (en) * 2017-09-12 2020-05-22 山东大学 Mxene-coated composite electrode material and preparation method thereof
CN107706372A (en) * 2017-09-12 2018-02-16 山东大学 A kind of combination electrode material of Mxene claddings and preparation method thereof
CN108336332A (en) * 2018-01-22 2018-07-27 山西大学 A kind of tin dioxide powder and preparation method thereof
CN108910940A (en) * 2018-07-16 2018-11-30 杭州电子科技大学 A kind of online cracking atomization composite precursor preparation SnO2The method of/amorphous carbon nano-composite material
CN110061234A (en) * 2019-05-27 2019-07-26 河南科技学院 A kind of anode material for lithium-ion batteries and preparation method thereof
CN110061234B (en) * 2019-05-27 2021-06-04 河南科技学院 Lithium ion battery anode material and preparation method thereof
CN111554868A (en) * 2020-04-07 2020-08-18 湖南大学 Power battery material with core-shell structure and preparation method thereof
CN111554868B (en) * 2020-04-07 2022-07-05 湖南大学 Power battery material with core-shell structure and preparation method thereof
CN112467127A (en) * 2020-09-24 2021-03-09 陕西红马科技有限公司 Coating modified lithium ion ternary cathode material and preparation method thereof
CN112186167A (en) * 2020-10-28 2021-01-05 陕西彩虹新材料有限公司 Preparation method of template-method-coated high-nickel ternary cathode material for lithium ion battery
CN113871209A (en) * 2021-08-30 2021-12-31 兰州大学 Carbon-coated graphene-iron oxide composite electrode material and preparation method and application thereof
CN113871209B (en) * 2021-08-30 2023-05-26 兰州大学 Carbon-coated graphene-ferric oxide composite electrode material and preparation method and application thereof
CN114368787A (en) * 2022-01-10 2022-04-19 东华大学 High-conductivity and high-stability lithium manganate material and application thereof
CN114368787B (en) * 2022-01-10 2023-10-27 东华大学 High-conductivity and high-stability lithium manganate material and application thereof

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Application publication date: 20120718