CN110380035A - A kind of preparation method of the slurry for preparing negative electrode material and negative electrode material - Google Patents

A kind of preparation method of the slurry for preparing negative electrode material and negative electrode material Download PDF

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Publication number
CN110380035A
CN110380035A CN201910668420.XA CN201910668420A CN110380035A CN 110380035 A CN110380035 A CN 110380035A CN 201910668420 A CN201910668420 A CN 201910668420A CN 110380035 A CN110380035 A CN 110380035A
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negative electrode
electrode material
slurry
preparation
suspension
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CN110380035B (en
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何伟东
陈东江
丁显波
陈太宝
袁博韬
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Shenzhen Lithium Sulfur Technology Co Ltd
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Shenzhen Lithium Sulfur Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, and the slurry includes the following components'mass percentage: organic solvent 90%-99.98%, active material 0.02%-10%；The organic solvent includes the combination of oleyl amine, polyethylene glycol, oleic acid and octadecylene at least two；The active material be di-iron trioxide, iron hydroxide, can thermally decompose be one of ferric source organic matter or inorganic matter of di-iron trioxide or iron hydroxide or at least two mixing.Cathode material preparation method simple process provided by the invention, it is easy to implement, be conducive to improve production efficiency, save production cost, the comprehensive performance of the negative electrode material is better than traditional business C-material electrode.Therefore Fe is utilized3The battery that the electrode material of C preparation is assembled into has high circulation stability, high rate capability, and the battery safety significantly increased.

Description

A kind of preparation method of the slurry for preparing negative electrode material and negative electrode material
Technical field
The preparation side of technical field of lithium batteries of the present invention more particularly to a kind of slurry for preparing negative electrode material and negative electrode material Method.
Background technique
Lithium ion battery is due to having many advantages, such as that zero memory effect, low self-discharge are early widely used to various portable electrics In sub- equipment and electric car, but the chemical property of battery is but often limited to the performance of electrode, therefore finds one kind It is our institute's facing challenges with high-performance, high circulation, powerful new electrode materials.Commercial battery cathode material at present Material is carbon.Its limited energy density (372mAh g-1) cannot expire with poor forthright again, thermal stability and mechanical performance Pursuit of the sufficient people increasingly to high capacity, high performance battery completely.Therefore, research and development have high capacity, high thermal stability, stronger machine Tool performance and cheap new material are to the security performance limited and further promote battery for breaking through existing energy density It has a very important significance.Generally, the Mechanism of electrochemical behaviors of anhydrous of cell negative electrode material can be divided into following three kinds.Emerging two dimension Material, such as graphene (graphene), conductivity (~106S m-1) than conventional graphite (~105S m-1) the high number of electrode Magnitude, this results in the high rate performances being obviously improved, it is considered to be the electrode of following optimal potentiality.However one of them is serious Challenge be complicated and high cost of manufacture, and be unable to large-scale industry volume production limit his industry/be commercialized into Journey.Transition-metal oxide, including transiton metal binary oxides (CuO, Fe3O4, NiO etc.) with ternary transition-metal oxide (ZnFe2O4、Zn2SnO4、Co2MnO4Deng) material then theoretical capacity (500-1000mAh g with higher-1) and obtained very much The concern of researcher.But in charge and discharge process, transition-metal cation is implanted in Li2Further reaction generates in the structure cell of O Metal simple-substance.However the significant challenge of transition metal oxide is in its electrochemical reaction that huge volume change cannot be guaranteed The integrality of the structure of material.Often along with the powdered of active material in charge and discharge process, therefore cause serious appearance Amount decaying and safety problem.In addition, the poor electronics coefficient of conductivity is but also its cycle life extremely has with charge/discharge capacity Limit.On the other hand, the materials such as Si, Sn and Ge due to can during charge and discharge lithiumation and lithium ion formed alloy thus can release Put biggish capacity.However it limits Si electrode further commercialized obstacle is also body in its charge and discharge process close to 400% Product variation.Its huge volume change makes particle powder and cannot be guaranteed the integrality of SEI membrane structure.Fe3C and its spread out Biology becomes the coke of people's research due to its preferable chemical stability, high conductivity (~106S m-1) and mechanical strength Point.But existing method and the Fe of raw material preparation3The comprehensive performance of C and its derivative is bad, to limit Fe3C and its derivative Application of the object in lithium battery.
Therefore, the prior art is defective, needs to improve.
Summary of the invention
The technical problem to be solved by the present invention is providing the preparation side of a kind of slurry for preparing negative electrode material and negative electrode material Method makes the battery dressed up have high circulation stability, high rate capability, and the battery safety significantly increased.
Technical scheme is as follows: the preparation method of a kind of slurry preparing negative electrode material and negative electrode material is provided, The slurry includes the following components'mass percentage:
Organic solvent 90%-99.98%,
Active material 0.02%-10%.
The organic solvent includes the combination of oleyl amine, polyethylene glycol, oleic acid and octadecylene at least two；The active material For di-iron trioxide, iron hydroxide, can to thermally decompose be the ferric source organic matter of di-iron trioxide or iron hydroxide or inorganic One of object or at least two mixing.
The preparation method, includes the following steps.
S1: weighing organic solvent and active material in mass ratio, and be packed into and mixed in a reservoir, and acquisition prepares lithium electricity The slurry of pond negative electrode material.
S2: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 1kpa- 10kpa, and inert gas is passed through after stable 10min-100min at room temperature, obtain the first suspension.
S3: the first suspension prepared in step S2 is under the atmosphere of inert gas in 80 DEG C~180 DEG C stirring 10s ~60min forms the second suspension of stable uniform.In this step, it is still in the environment of inert gas；If step S1 In use be ferric source organic matter or inorganic matter, ferric source organic matter or inorganic matter will decompose at 80 DEG C~180 DEG C Uniformly divide by step S2 and step S3 at di-iron trioxide or iron hydroxide at di-iron trioxide or iron hydroxide It dissipates in organic solvent.Anhydrous and oxygen-free technology can promote di-iron trioxide or iron hydroxide in the uniformity of organic solvent dispersion； And it is mixed in the state of heating, can effectively promote the uniformity of mixing.
S4: the second suspension in step S3 is under the atmosphere of inert gas and to 200 DEG C~450 DEG C and is being heated 0.1h~4h obtains third suspension.In this step, high temperature will be such that organic solvent cracks, and pyrolysis product is attached to three oxidations Two iron or iron hydroxide particle surface.In this step, it is still in the environment of inert gas.Step S1-S4 is same It is carried out in one container, can effectively simplify operating procedure, facilitate operation.Step S2-S4 is isolating oxygen under an inert gas Gas avoids organic solvent from being oxidized in Pintsch process.
S5: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, by solid Component dry 1h-36h under 50 DEG C of -130 DEG C of ranges, obtains solid particle.
S6: by the high-temperature heat treatment under inert gas protection of solid particle obtained in step S5, it is heat-treated duration 0.5h- 6h, the temperature of heat treatment are 800 DEG C~1300 DEG C, obtain lithium cell cathode material.Pyrolysis product aoxidizes two for three at high temperature Iron or iron hydroxide are reduced into Fe, and Fe, which is further reacted with pyrolysis product, generates carbon coating Fe3C, carbon nanomaterial.
Further, the organic or particles of inorganic material of the ferric source are as follows: ferric perchlorate, ferric acetyl acetonade, carbonyl iron One of or at least two combination, the partial size of the di-iron trioxide and iron hydroxide is 30nm~90nm.
Further, lithium cell cathode material is carbon coating Fe3C, carbon nanomaterial mixture；The partial size of the mixture No more than 50nm, Fe3C crystal structure is rhombic form, and the carbon and carbon nanomaterial of cladding are hexagonal structure；The carbon coating Fe3C is core-shell structure.
Further, the step S2 are as follows: take out the container of the slurry in step S1 comprising preparing lithium cell cathode material Vacuum is passed through inert gas to negative pressure 2kpa-3kpa at room temperature after stable 30min-60min, obtain the first suspension.
Further, the step S3 are as follows: by the first suspension prepared in step S2 in 110 DEG C~160 DEG C stirring 20s ~30min forms the second suspension of stable uniform.
Further, the step S4 are as follows: the second suspension in step S3 to 250 DEG C~350 DEG C and is being heated into 1h ~h obtains third suspension.
Further, the step S5 are as follows: third suspension prepared by step S4 is separated by solid-liquid separation, solid group is assigned to Point and liquid component, by solid component under 80 DEG C of -100 DEG C of ranges dry 18h-24h, obtain solid particle.
Further, the step S6 are as follows: by the high warm under inert gas protection of solid particle obtained in step S5 Processing is heat-treated duration 1.5h-2h, and the temperature of heat treatment is 900 DEG C~1200 DEG C, obtains the lithium ion battery anode material of core-shell structure Material.
Carbon coating Fe3C is high since its preferable chemical stability, high conductivity can meet the application in lithium battery What conductivity was obviously improved the high rate performance of battery.The ferro element and carbon of earth rich reserves make carbon coating Fe3C material Expect cheap and is easy to produce.Additionally, due in forming process, C atom occupies the gap of Fe structure cell and results in d- layers Electrical attraction, the activation energy that can reduce battery electrode reaction, make battery have higher capacity.Due to a Fe3C structure cell can only Store 1/6 lithium ion, therefore Fe3C can in electrode section SEI film component lipid and ethers offer energy is be provided, Make battery that there is higher capacity, therefore utilizes carbon coating Fe3The battery that the electrode material of C preparation is assembled into is stablized with high circulation Property, high rate capability, and the battery safety significantly increased.
Using the above scheme, the present invention provides the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, system Standby carbon coating Fe3C chemical stability, high conductivity can meet to be applied in lithium battery, what high conductivity was obviously improved The high rate performance of battery.Therefore the battery that prepared by the method electrode material is assembled into has high circulation stability, high power Rate performance, and the battery safety significantly increased.
Detailed description of the invention
Fig. 1 is the SEM figure for the negative electrode material that the embodiment of the present invention 1 obtains；
Fig. 2 is the TEM figure for the negative electrode material that the embodiment of the present invention 1 obtains；
Fig. 3 is the HR-TEM figure for the negative electrode material that the embodiment of the present invention 1 obtains；
Fig. 4 be the embodiment of the present invention 1 obtain material be cathode, lithium be anode in 1M LiPF6It is formed under electrolyte The CV of half-cell schemes；
Fig. 5 be the embodiment of the present invention 1 obtain material be cathode, lithium be anode different electrolytes composition half-cell EIS figure；
Fig. 6 be the embodiment of the present invention 1 obtain material be cathode, lithium be anode different electrolytes composition half-cell CV figure；
Fig. 7 be the embodiment of the present invention 1 obtain material be cathode, lithium be anode in 1M LiPF6The half of electrolyte composition The circulation figure of battery.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The present invention provides the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, and the slurry includes following The component of mass percent:
Organic solvent 99.91%,
Active material 0.09%；
The organic solvent is the combination of 50wt% oleic acid and octadecylene 50wt%；The active material is acetylacetone,2,4-pentanedione Iron.
The preparation method of the negative electrode material, comprising the following steps:
S1: weighing organic solvent and active material in mass ratio, and be packed into and mixed in a reservoir, and acquisition prepares lithium electricity The slurry of pond negative electrode material.
S2: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 3kpa, and Argon gas is passed through after stable 40min at room temperature, obtains the first suspension.
S3: the first suspension prepared in step S2 is under the atmosphere of inert gas in 110 DEG C of stirring 25min, shape At the second suspension of stable uniform.
S4: the second suspension in step S3 being under the atmosphere of inert gas and to 285 DEG C and heating 1.5h, is obtained Third suspension.
S5: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, by solid Component drying at 90 DEG C for 24 hours, obtains solid particle.
By solid particle obtained in step S5, high-temperature heat treatment, heat treatment duration 2h are heat-treated S6 under protection of argon gas 900 DEG C of temperature, the lithium cell cathode material of acquisition, partial size 40nm-50nm.
Referring to Fig. 1, Fig. 1 is the scanning electron microscope (SEM) photograph (SEM figure) for the negative electrode material that the present embodiment obtains；Fig. 2 is this implementation The transmission electron microscope picture (TEM figure) for the negative electrode material that example obtains；Fig. 3 is the high power transmission electron microscope for the negative electrode material that the present embodiment obtains Scheme (HR-TEM figure) and selective electron diffraction figure (SEAD figure).It will be seen from figure 1 that negative electrode material manufactured in the present embodiment is Spherical particle and strip particle, anhydrous and oxygen-free technology can promote di-iron trioxide or iron hydroxide in the uniform of organic solvent dispersion Property, after thermal reduction processing, the carbon coating Fe of formation3C particle can be uniformly dispersed in C-material substrate, and remain nanometer The shape of grain.The catalytic effect of Fe is also catalyzed C and forms nano-carbon layer, further increases the electric conductivity of electrode.
Referring to Fig. 2, as can be seen that nano-carbon layer coats Fe from the TEM figure of Fig. 23C forms carbon coating Fe3C nano Core-shell structure.
Referring to Fig. 3, Fig. 3 is the HR-TEM test result for the negative electrode material that the present embodiment obtains, the lattice item of 0.33nm The right Fe of line3(020) crystal face of C particle, the right nano-carbon layer of the lattice fringe of 0.34nm (004) crystal face.SAED diffraction Figure then demonstrates Fe3C/C particle has good crystallinity.From HR-TEM figure and SEAD figure it can be seen that Fe3C crystal structure is Rhombic form, the carbon of cladding are hexagonal structure.As can be seen from the figure Fe3The crystallization degree of C and nano-carbon layer is all very high.
Referring to Fig. 4, the material that Fig. 4 is the present embodiment acquisition is cathode, lithium is anode in 1M LiPF6Electrolyte the following group At half-cell CV figure；The half-cell first lap formed stablize to SEI after, the 2nd, 3 circle CV curves be almost overlapped, this The negative electrode material for demonstrating the present embodiment acquisition has good electrochemistry and structural stability.
Referring to Fig. 5, the material that Fig. 5 is the present embodiment acquisition is cathode, lithium is anode the half of different electrolytes composition The EIS of battery schemes；The negative electrode material that the present embodiment obtains is in 1M LiPF6There is the smallest semicircle radius, this proof under electrolyte In 1M LiPF6Interface impedance under electrolyte is minimum.The negative electrode material that the present embodiment obtains is in 2M LiPF6With 1M LiClO4 Interfacial migration resistance under electrolyte is almost the same.
Referring to Fig. 6, the material that Fig. 6 is the present embodiment acquisition is cathode, lithium is anode the half of different electrolytes composition The CV of battery schemes.It can be seen from the figure that there is apparent differences for the CV figure under different electrolytes.1M LiPF6With 2M LiPF6The position of lower the occurred redox peaks of electrolyte is roughly the same.And in 1M LiClO4Oxidation appeared in electrolyte There are significant changes for the position of reduction peak.Illustrate carbon coating Fe3The catalytic of the electrode of C to the F element in electrolyte exist compared with Strong correlation.
Referring to Fig. 7, the material that Fig. 7 is the present embodiment acquisition is cathode, lithium is anode in 1M LiPF6Electrolyte composition Half-cell circulation figure.Core-shell structure Fe prepared by the present embodiment3C/C nano material, good structural retention with Electric conductivity is the capacity that battery has 480mAh g-1 under the high current density of 2A g-1, and 1000 circle of circulation still remains 95% efficiency for charge-discharge.This demonstrate that Fe3The stability of C/C nano-electrode material structure.
Embodiment 2
The present invention provides the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, and the slurry includes following The component of mass percent:
Organic solvent 99.6%,
Active material 0.4%；
The organic solvent is the combination of 40wt% polyethylene glycol and 60wt% octadecylene；The active material is hydroxide Iron.
The preparation method of the negative electrode material, comprising the following steps:
S1: weighing organic solvent and active material in mass ratio, and be packed into and mixed in a reservoir, and acquisition prepares lithium electricity The slurry of pond negative electrode material.
S2: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 2kpa, and Argon gas is passed through after stable 40min at room temperature, obtains the first suspension.
S3: the first suspension prepared in step S2 is under the atmosphere of inert gas in 110 DEG C of stirring 15min, shape At the second suspension of stable uniform.
S4: the second suspension in step S3 being under the atmosphere of inert gas and to 300 DEG C and heating 1h, obtains the Three suspensions.
S5: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, by solid Component dry 18h at 80 DEG C, obtains solid particle.
The high-temperature heat treatment under protection of argon gas of solid particle obtained in step S5 is heat-treated duration 1.5h by S6, at heat 1000 DEG C of the temperature of reason, the lithium cell cathode material of acquisition, partial size 38nm-47nm.
Embodiment 3
The present invention provides the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, and the slurry includes following The component of mass percent:
Organic solvent 95%,
Active material 5%；
The organic solvent is the combination of 60wt% oleic acid and 40wt% polyethylene glycol；The active material is carbonyl iron.
The preparation method of the negative electrode material, comprising the following steps:
S1: weighing organic solvent and active material in mass ratio, and be packed into and mixed in a reservoir, and acquisition prepares lithium electricity The slurry of pond negative electrode material.
S2: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 3kpa, and Argon gas is passed through after stable 60min at room temperature, obtains the first suspension.
S3: the first suspension prepared in step S2 is under the atmosphere of inert gas in 160 DEG C of stirring 30min, shape At the second suspension of stable uniform.
S4: the second suspension in step S3 being under the atmosphere of inert gas and to 250 DEG C and heating 2h, obtains the Three suspensions.
S5: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, by solid Component dry 23h at 100 DEG C, obtains solid particle.
By solid particle obtained in step S5, high-temperature heat treatment, heat treatment duration 2h are heat-treated S6 under protection of argon gas 900 DEG C of temperature, the lithium cell cathode material of acquisition, partial size 40nm-50nm.
Embodiment 4
The present invention provides the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, and the slurry includes following The component of mass percent:
Organic solvent 98%,
Active material 2%；
The organic solvent is the combination of 65wt% oleic acid and 35wt% polyethylene glycol；The active material is three oxidations two Iron.
The preparation method of the negative electrode material, comprising the following steps:
S1: weighing organic solvent and active material in mass ratio, and be packed into and mixed in a reservoir, and acquisition prepares lithium electricity The slurry of pond negative electrode material.
S2: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 3kpa, and Argon gas is passed through after stable 30min at room temperature, obtains the first suspension.
S3: the first suspension prepared in step S2 is under the atmosphere of inert gas in 110 DEG C of stirring 20min, shape At the second suspension of stable uniform.
S4: the second suspension in step S3 being under the atmosphere of inert gas and to 350 DEG C and heating 1.5h, is obtained Third suspension.
S5: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, by solid Component drying at 90 DEG C for 24 hours, obtains solid particle.
By solid particle obtained in step S5, high-temperature heat treatment, heat treatment duration 2h are heat-treated S6 under protection of argon gas 1200 DEG C of temperature, the lithium cell cathode material of acquisition, partial size 30nm-40nm.
Embodiment 5
The present invention provides the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, and the slurry includes following The component of mass percent:
Organic solvent 99.95%,
Active material 0.05%；
The organic solvent is the combination of 55wt% oleic acid and 45wt% polyethylene glycol；The active material is perchloric acid Iron.
The preparation method of the negative electrode material, comprising the following steps:
S1: weighing organic solvent and active material in mass ratio, and be packed into and mixed in a reservoir, and acquisition prepares lithium electricity The slurry of pond negative electrode material.
S2: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 3kpa, and Argon gas is passed through after stable 40min at room temperature, obtains the first suspension.
S3: the first suspension prepared in step S2 is under the atmosphere of inert gas in 110 DEG C of stirring 2min, is formed Second suspension of stable uniform.
S4: the second suspension in step S3 being under the atmosphere of inert gas and to 265 DEG C and heating 1.5h, is obtained Third suspension.
S5: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, by solid Component drying at 90 DEG C for 24 hours, obtains solid particle.
By solid particle obtained in step S5, high-temperature heat treatment, heat treatment duration 2h are heat-treated S6 under protection of argon gas 1000 DEG C of temperature, the lithium cell cathode material of acquisition, partial size 27nm-40nm.
Embodiment 6
The present invention provides the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, and the slurry includes following The component of mass percent:
Organic solvent 91%,
Active material 9%；
The organic solvent is the combination of 40wt% oleic acid and 60wt% octadecylene；The active material is acetylacetone,2,4-pentanedione Iron.
The preparation method of the negative electrode material, comprising the following steps:
S1: weighing organic solvent and active material in mass ratio, and be packed into and mixed in a reservoir, and acquisition prepares lithium electricity The slurry of pond negative electrode material.
S2: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 3kpa, and Argon gas is passed through after stable 40min at room temperature, obtains the first suspension.
S3: the first suspension prepared in step S2 is under the atmosphere of inert gas in 110 DEG C of stirring 25min, shape At the second suspension of stable uniform.
S4: the second suspension in step S3 being under the atmosphere of inert gas and to 285 DEG C and heating 1.5h, is obtained Third suspension.
S5: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, by solid Component drying at 90 DEG C for 24 hours, obtains solid particle.
By solid particle obtained in step S5, high-temperature heat treatment, heat treatment duration 2h are heat-treated S6 under protection of argon gas 900 DEG C of temperature, the lithium cell cathode material of acquisition, partial size 40nm-50nm.
Following table is the negative electrode material that embodiment 1-6 is obtained and graphitic carbon is cathode, lithium is anode in 1MLiPF6 electrolyte The comparison of the capacity and efficiency for charge-discharge of the half-cell of composition.
In conclusion the present invention provides the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, preparation Carbon coating Fe3C chemical stability, high conductivity can meet to be applied in lithium battery, what high conductivity was obviously improved battery High rate performance.Therefore the battery that prepared by the method electrode material is assembled into has high circulation stability, high power forthright Can, and the battery safety significantly increased.
The above is merely preferred embodiments of the present invention, be not intended to restrict the invention, it is all in spirit of the invention and Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within principle.

Claims (8)

1. the preparation method of a kind of slurry for preparing negative electrode material and negative electrode material, which is characterized in that the slurry includes following The component of mass percent:
Organic solvent 90%-99.98%,
Active material 0.02%-10%；
The organic solvent includes the combination of oleyl amine, polyethylene glycol, oleic acid and octadecylene at least two；The active material is three It aoxidizes two iron, iron hydroxide, can thermally decompose as in the ferric source organic matter or inorganic matter of di-iron trioxide or iron hydroxide One kind or at least two mixing；
The preparation method, comprising the following steps:
S1: organic solvent and active material are weighed in mass ratio, and is packed into and is mixed in a reservoir, it is negative that acquisition prepares lithium battery The slurry of pole material；
S2: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 1kpa-10kpa, and Inert gas is passed through after stable 10min-100min at room temperature, obtains the first suspension；
S3: the first suspension prepared in step S2 is under the atmosphere of inert gas 80 DEG C~180 DEG C stirring 10s~ 60min forms the second suspension of stable uniform；
S4: the second suspension in step S3 is under the atmosphere of inert gas to 200 DEG C~450 DEG C and heat 0.1h~ 4h obtains third suspension；
S5: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, by solid component Dry 1h-36h, obtains solid particle under 50 DEG C of -130 DEG C of ranges；
The high-temperature heat treatment under inert gas protection of solid particle obtained in step S5 is heat-treated duration 0.5h-6h, heat by S6 The temperature of processing is 800 DEG C~1300 DEG C, the lithium cell cathode material of acquisition.
2. the preparation method of a kind of slurry for preparing negative electrode material according to claim 1 and negative electrode material, feature exist In the organic matter or inorganic matter of the ferric source are as follows: one of ferric perchlorate, ferric acetyl acetonade, carbonyl iron or at least The partial size of two kinds of combination, the di-iron trioxide and iron hydroxide is 30nm~90nm.
3. the preparation method of a kind of slurry for preparing negative electrode material according to claim 1 and negative electrode material, feature exist In lithium cell cathode material is carbon coating Fe3C, carbon nanomaterial mixture；The partial size of the mixture is no more than 50nm, Fe3C Crystal structure is rhombic form, and the carbon and carbon nanomaterial of cladding are hexagonal structure；The carbon coating Fe3C is core-shell structure.
4. the preparation method of a kind of slurry for preparing negative electrode material according to claim 1 and negative electrode material, feature exist In the step S2 are as follows: by the container vacuum-pumping of the slurry in step S1 comprising preparing lithium cell cathode material to negative pressure 2kpa- 3kpa, and inert gas is passed through after stable 30min-60min at room temperature, obtain the first suspension.
5. the preparation method of a kind of slurry for preparing negative electrode material according to claim 1 and negative electrode material, feature exist In the step S3 are as follows: by the first suspension prepared in step S2 in 110 DEG C~160 DEG C stirring 20s~30min, formed steady Fixed the second uniform suspension.
6. the preparation method of a kind of slurry for preparing negative electrode material according to claim 1 and negative electrode material, feature exist In the step S4 are as follows: the second suspension in step S3 to 250 DEG C~350 DEG C and is being heated 1h~2h, it is outstanding to obtain third Turbid.
7. the preparation method of a kind of slurry for preparing negative electrode material according to claim 1 and negative electrode material, feature exist In the step S5 are as follows: third suspension prepared by step S4 is separated by solid-liquid separation, solid component and liquid component are assigned to, Solid component is dried into 18h-24h under 80 DEG C of -100 DEG C of ranges, obtains solid particle.
8. the preparation method of a kind of slurry for preparing negative electrode material according to claim 1 and negative electrode material, feature exist In the step S6 are as follows: by the high-temperature heat treatment under inert gas protection of solid particle obtained in step S5, be heat-treated duration 1.5h-2h, the temperature of heat treatment are 900 DEG C~1200 DEG C, obtain the lithium cell cathode material of core-shell structure.
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US20140220479A1 (en) * 2013-02-05 2014-08-07 Uwm Research Foundation Advanced electrocatalysts for oxygen reduction reaction
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CN104269566A (en) * 2014-09-22 2015-01-07 南开大学 Preparation method and application of nitrogen-doped porous carbon nano sheet composite material
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