CN106469814B - A kind of covering, negative electrode material, lithium ion battery and preparation method thereof - Google Patents
A kind of covering, negative electrode material, lithium ion battery and preparation method thereof Download PDFInfo
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- CN106469814B CN106469814B CN201610231149.XA CN201610231149A CN106469814B CN 106469814 B CN106469814 B CN 106469814B CN 201610231149 A CN201610231149 A CN 201610231149A CN 106469814 B CN106469814 B CN 106469814B
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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
- H01M4/58—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of coverings, negative electrode material, lithium ion battery and preparation method thereof.Covering includes: graphene, water-insoluble carbon matrix precursor, dispersing agent；The dispersing agent is one of amino silane, epoxy radicals silicone hydride, polyvinyl alcohol or a variety of.Negative electrode material is mainly made of graphite and the covering.Micro- capacitor theory that covering of the invention mainly uses graphene and amorphous carbon to be constituted, greatly improves the capacitance and cycle-index of lithium ion battery.
Description
Technical field
The present invention relates to electrode material technical field, more particularly, to a kind of covering, negative electrode material, lithium ion battery and
Preparation method.
Background technique
Lithium ion battery refers to the general name with lithium ion inlaid scheme for positive material cell, with the compound containing lithium
Make anode, exists without lithium metal, only lithium ion.The charge and discharge process of lithium ion battery is exactly the insertion of lithium ion and is taken off
Embedding process.During the insertion of lithium ion and deintercalation, the insertion and deintercalation of simultaneous and lithium ion equivalent electronics.
For negative electrode of lithium ion battery, graphite is a kind of ideal material.Graphite has good electric conductivity,
Crystallinity is high, at low cost, and bulk density is high, and it is the pith of current lithium ion battery negative material that theoretical embedding lithium capacity is high.
But there are some disadvantages, such as poor with compatibility of electrolyte, first charge-discharge reversible capacity is low, is not suitable for large current density
Electricity, poor circulation.
In order to solve the disadvantages mentioned above of graphite material, people are by various methods modified graphite.Common modification
Method is to be mixed into negative electrode material using carbon matrix precursors such as pitch, resins as coating or covering, using carbonization.More than
Modified, capacitance, the cycle-index of graphite cathode make moderate progress, but improvement is not significant, and market significance is little.
Summary of the invention
The first object of the present invention is to provide a kind of covering, and the covering can efficiently improve lithium ion battery
The capacitance and cycle-index of cathode.
The second object of the present invention is to provide a kind of negative electrode material, and the negative electrode material has that capacitance is high, circulation
Often, steady performance.
The third object of the present invention is to provide a kind of preparation method of negative electrode material, and there are many preparation methods,
All have the advantages that process is simple, controllability is strong, high production efficiency.
The fourth object of the present invention is to provide a kind of lithium ion battery, and the battery has that capacitance is high, circulation time
More, the steady performance of number, has broader practice prospect.
In order to solve the above technical problems, the present invention provides following technical schemes:
A kind of covering, comprising: graphene, water-insoluble carbon matrix precursor, dispersing agent；The dispersing agent is amino silicone
One of alkane, epoxy radicals silicone hydride, polyvinyl alcohol are a variety of.
The covering is mainly used for being modified the cathode of lithium ion battery, has and also is likely used for other unknown fields.
Compared with existing negative electrode of lithium ion battery modified material, which mainly increases dispersing agent, to solve
The dispersion of graphene and carbon matrix precursor, to further improve the capacity and cycle-index of electrode material.
Wherein, the consistency problem of carbon matrix precursor and dispersing agent is extremely important to modified effect, and the present invention has selected non-aqueous
The carbon matrix precursor of dissolubility, and the dispersing agents such as amino silane of arranging in pairs or groups, epoxy radicals silicone hydride, polyvinyl alcohol, solve the above problem.
It is irreversible when the present invention is used for the cathode of lithium ion battery compared with the modifying agent for being not added with dispersing agent through counting
Capacity reduces 5% or more；Compared with the graphite cathode for being not added with any modifying agent, irreversible capacity reduces 10% or more,
Cycle life and stability improve 30% or more.
Graphene of the present invention includes graphene nano lamella and graphene, further comprises that biomass graphene is received
Rice lamella and biomass graphene.
Graphene of the present invention can be obtained by different preparation methods, such as mechanical stripping method, epitaxial growth method, change
Vapor deposition method is learned, graphite oxidation reduction method can also be by biomass resource hydrothermal carbonization method, and in the prior art
The graphene of other method preparations.But some methods are difficult to realize large scale preparation and obtain the theoretic graphite of stricti jurise
It is different there are certain impurity elements, other homoatomics of carbon in alkene, such as the obtained graphene of a part of prior art preparation
Body or the non-single layer of the number of plies even graphene-structured (such as 3 layers, 5 layers, 10 layers, 20 layers etc.) of multilayer, what the present invention was utilized
Graphene also includes the graphene on above-mentioned non-critical theory of meaning.
Jinan holy well company technique can be used in graphene nano lamella, using agriculture and forestry organic waste material as primary raw material, by hydrolyzing,
Catalytic treatment, heat treatment and etc. obtain have excellent conductive property multiporous biological matter graphene complex, main feature
It is between 1~10 layer for contained graphene number of plies, non-carbon nonoxygen element content is 0.5wt%~6wt%.
Above-mentioned covering can also be further improved:
Further, the carbon matrix precursor be preferably phenolic resin, Lauxite, furane resins, epoxy resin, in pitch
It is one or more.
The above carbon matrix precursor is formed by amorphous structure after being carbonized and enriches, and is more advantageous to the insertion of lithium ion and takes off
It is embedding, the consumption of lithium ion when forming SEI film when decreasing initial charge.Specifically, the above resin further selects thermosetting property
Resin, further select in high molecular weight resin, the preferred thermoset pitch of pitch.
Further, by weight, the graphene accounts for the 0.1-5% of covering total amount, preferred 0.5-3%, into one
Walk preferred 1-2%；The dispersing agent accounts for the 0.05-0.5% of covering total amount, preferred 0.05-0.3%, further preferably
0.05-0.1%.
Having a major impact with comparison modified effect for each raw material, when being mixed with aforementioned proportion, is uniformly dispersed, and the effect that is carbonized
It is good, more conducively improve capacity and the service life of battery.
Further, further include curing agent for the carbon matrix precursor.
The setting that curing agent is conducive to the carbon matrix precursor is added, the type and dosage of curing agent are selected according to carbon matrix precursor
It selects, such as when carbon matrix precursor is thermosetting resin, available curing agent has hexamethylenetetramine, 3- diethyl amino propylamine, three
Methyl hexamethylene diamine, dihexyl triamine etc..
Further, in dispersing agent, amino silane, epoxy radicals silicone hydride respectively refer to any silicon containing amino or epoxy group
Alkane, such as epoxy group trimethoxysilane coupling agent etc..It is further silane coupling agent 3- urea propyl-triethoxysilicane etc..
In addition, the present invention provides a kind of negative electrode material, mainly it is made of graphite and covering described above.
The negative electrode material uses common graphite as active material, then cooperates covering of the invention, will be than traditional
Negative electrode material has higher capacitance and cycle-index.Equally, the negative electrode material is mainly used for lithium ion battery at present, but
It is possibly used for the battery of other UNKNOWN TYPEs.When being used for lithium ion battery, available positive electrode has LiMn2O4, cobalt acid lithium
Or LiFePO4 etc..
The above negative electrode material can be further improved, such as:
Further, by weight, the covering, the graphite proportion be 3-15:85-97.
In contrast, the cathode of the above ratio can give full play to the modified effect of covering of the invention, preferably 5-10:
90-95, further 5-8:90-93.It, can also be using except range if consider the other factors such as cost, potential certainly
Proportion.
In addition, covering of the present invention can each raw material independent packaging, it is current existing mixed；Storage can also directly be mixed
It deposits, this is mainly depending on the requirements such as storage, transport.When being mixed and made into negative electrode material with graphite, can use with lower section
One of formula:
Mode one: the graphene, the carbon matrix precursor, the dispersing agent, the graphite are dissolved and is mixed in a solvent
Even, drying later is carbonized to obtain the final product；
Mode two: the graphene, the carbon matrix precursor, the dispersing agent are dissolved and is mixed in a solvent, through overdrying
It mixes, then is carbonized with graphite after dry to obtain the final product；
Wherein, when containing the curing agent in the covering, by the stone in the mode one and the mode two
Black alkene is additionally added the curing agent when dissolving in a solvent, and curing reaction is also carried out before the carbonization.
Both the above mode belongs to solwution method, and the difference of the two is that dry opportunity is different, i.e. drying can both be added
It carries out to carry out after graphite is added before graphite.The advantages of both modes is that equipment used is simple, and key point is mixed
Even step, to guarantee that each ingredient is uniformly dispersed mutually.Blending manner can be using a variety of, such as ball milling, and ball milling and dissolution can be same
Shi Jinhang, Ball-milling Time are generally 1-4h, are subject to mixing.
It can be during dissolution and mixing and stirred in charging, be also possible to dissolve respectively, then mixing one
It rises.
There are many kinds of drying means, and generally depending on the type of solvent, available method has heating evaporation etc..
When containing curing agent, the opportunity of curing reaction be before carburizing reagent, and both can be in mode one
After drying, it is also possible to after mixing and before dry；Both can be before admixed graphite in mode two, it can also be dry
After dry, it is also possible to after admixed graphite and before dry.
In addition, following preparation method also can be used in above-mentioned negative electrode material:
The graphene, the carbon matrix precursor, the dispersing agent are heated into kneading, cooling, add the graphite mixing,
By being carbonized to obtain the final product；
When containing the curing agent in the covering, it is additionally added the curing agent after the cooling, and
Curing reaction is also carried out before the carbonization.
This method belongs to fusion method, its advantage is that high production efficiency.Plurality of devices can be used in kneading described in it, such as flows
Become instrument etc..Preferably all raw materials are pre-mixed before the kneading.
The kneading condition is further are as follows: is mixed at 150 DEG C to balance with rheometer.
Carbonization of the present invention is further are as follows: carries out at 900 DEG C -1200 DEG C.
Curing reaction of the present invention is mainly depending on curing agent and resin type, and usually gradient-heated solidifies,
By taking phenolic resin as an example, condition of cure are as follows: 120-130 DEG C 60 minutes or so, 140-150 DEG C 60 minutes or so, 160-170 DEG C 30
Minute or so.
In addition to three kinds of preparation methods provided above, other preparation methods are can also be used in negative electrode material of the present invention.
The present invention also provides a kind of lithium ion battery, the cathode of the lithium ion battery is mainly by previously described cathode
Material is made.
Described above, which has higher capacitance than traditional lithium ion battery, more to recycle
Number, longer service life, more stable storage performance.
Compared with prior art, the present invention has following technical effect that
(1) dispersion effect of covering is good, can more improve the property such as capacitance, service life, stability of electrode material
Energy.
(2) capacitance height is provided, cycle-index is more, the stable negative electrode material of performance and battery.
(3) a variety of methods of preparation negative electrode material are provided, provide more more options for the producer.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments,
It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Prepare graphene A:
First prepare cellulose:
(1) dense for the formic acid of 80wt% and the organic acid solution pair of acetic acid using total acid by after wheat straw comminution pretreatment
Treated, and wheat straw carries out boiling, and the mass ratio of acetic acid and formic acid is 1:12 in the organic acid solution of the present embodiment, and is being added
Hydrogen peroxide (the H for accounting for wheat straw raw material 1wt% is added before entering raw material2O2) it is used as catalyst, 120 DEG C of reaction temperature are controlled, instead
30min, solid-liquid mass ratio 1:10 are answered, and obtained reaction solution is subjected to first time separation of solid and liquid；
(2) being separated by solid-liquid separation obtained solid for the first time, that total acid is added is dense for the formic acid of 75wt% and the organic acid solution of acetic acid
Acid elution is carried out, wherein joined the peroxide for accounting for wheat straw raw material 8wt% in the dense organic acid solution for 75wt% of above-mentioned total acid
Change hydrogen (H2O2) it as the mass ratio of catalyst and acetic acid and formic acid is 1:12, controlled at 90 DEG C, wash time 1h, solid-liquid
Mass ratio is 1:9, and reaction solution is carried out second and is separated by solid-liquid separation；
(3) it collects for the first time and is separated by solid-liquid separation obtained liquid for the second time, high temperature and pressure is carried out under 120 DEG C, 301kPa
Obtained formic acid and acetic acid vapor are condensed back into the reaction kettle of step (1) as cooking liquor, use until being evaporated by evaporation
Boiling in step (1)；
(4) it collects and is separated by solid-liquid separation obtained solid for the second time, and washed, control washing temperature is 80 DEG C, washing slurry
Dense is 6wt%, and obtained washing slurry is carried out third time separation of solid and liquid；
(5) it collects and is separated by solid-liquid separation obtained liquid for the third time, carry out water, sour rectifying, obtained mix acid liquor is back to step
Suddenly the boiling of step (1) is used in the reaction kettle of (1) as cooking liquor, obtained water to be back to step (5) and water is washed with water；
(6) it collects and is separated by solid-liquid separation obtained solid for the third time and is screened to obtain required screened stock cellulose.
Then graphene is prepared as raw material using the cellulose being prepared as above:
(1) 1:1 cellulose mixture and frerrous chloride in mass ratio, stirring carries out catalytic treatment 4h at 150 DEG C, it is dry extremely
Presoma moisture content 10wt%, obtains presoma；
(2)N2In atmosphere, presoma is warming up to 170 DEG C with 3 DEG C/min rate, keeps the temperature 2h, temperature programming later to 400
DEG C, 3h is kept the temperature, is warming up to 1200 DEG C later, obtains crude product after keeping the temperature 3h；The heating rate of described program heating is 15 DEG C/min；
(3) at 55-65 DEG C, by crude product through over-richness be 10% sodium hydroxide solution, 4wt% chlorohydric acid pickling after, water
It washes to obtain biomass graphene, is denoted as graphene A.
Prepare graphene B:
Using the method for embodiment 10 in the patent of Publication No. CN104724696A, specifically: stalk is collected, processing is dry
Small pieces are shredded into after net, is immersed in ethanol solution, is at the uniform velocity stirred 5 hours with the revolving speed of 100r/min；Then solution is shifted
Into supercentrifuge, revolving speed is set as 3000r/min, and centrifugation time is 20 minutes, after take the broken sample of lower layer.Normal temperature and pressure
Under, broken sample is fitted into the Tissue Culture Dish that diameter is 15cm, is placed in air inlet, adjust flow parameter, setting wind speed is 6m/
S, air quantity 1400m3/ h is kept for ventilation state 12 hours；Tube furnace is warming up to 1300 DEG C, is passed through inert gas shielding, keeps
30 minutes；Broken sample after drying is placed in tube furnace, heats 5 hours, after being cooled to room temperature, it is obvious to obtain overburden ratio
Biomass graphene is denoted as graphene B.
Prepare graphene C:
Using the method for embodiment 1 in the patent of Publication No. CN105217621A, specifically:
(1) by the mixing of 2g graphite powder and 3g potassium dithionate, 3g phosphorus pentoxide and the 12mL concentrated sulfuric acid in reactor
It reacts in system, is stirred 4 hours under 80 DEG C of water bath conditions, until forming dark blue solution, obtain pre- oxygen after cooling, suction filtration, drying
The graphite of change；
(2) take graphite oxide 2g obtained by step (1) in three-neck flask, it is dense with 150mL under conditions of ice-water bath
Sulfuric acid solution is gradually added into the potassium permanganate of 25g, stirs 2 hours；
(3) three-neck flask of above-mentioned steps (2) is transferred to oil bath, is warming up to 35 DEG C, stirred 2 hours, continue stirring and by
The mixed solution of 30wt% hydrogen peroxide and deionized water is added according to the amount that volume ratio is 1:15；It filters, respectively with 4mL mass point
Number cleans 1 time for 10% dilute hydrochloric acid and deionized water, and centrifugation obtains the graphene oxide aoxidized for the first time after dry；
(4) the graphene oxide 2g prepared in step (3) is molten with the concentrated sulfuric acid of 50mL under conditions of ice-water bath again
Liquid is mixed in three-neck flask, is gradually added into the KMnO of 8g4, stir 1 hour；
(5) three-neck flask of above-mentioned steps (4) is transferred to oil bath, is warming up to 40 DEG C, stirred 1 hour, then proceed to heat up
To 90 DEG C, after stirring 1 hour, continues stirring and 30wt% hydrogen peroxide and deionized water is added according to the amount that volume ratio is 1:7
Mixed solution, it is cooling after continuing stirring 6 hours, filter, respectively with 4mL mass fraction be 10% dilute hydrochloric acid and deionized water
Cleaning 2 times, centrifugation obtain the graphene oxide of size uniformity after dry, are denoted as graphene C.
It is that embodiment percentage is weight percentage below.
Embodiment 1
1. compound
Holy well phenolic resin PF9503 is dissolved in ethyl alcohol, add silane coupling agent 3- urea propyl-triethoxysilicane and
Trimethylhexamethylenediamine.Mixture is carried out ball milling 2 hours.Graphene A is gradually added portionwise in ball milling system, is protected
Holding mill 2 hours.In final mixture, graphene content is 1%, and silane contents are about 0.05%, tri-methyl hexamethylene two
Amine additional amount is calculated according to the practical hydroxyl value of phenolic resin.
2. cladding
Spherical graphite powder is added in above-mentioned system and carries out ball milling, graphite solid content in total system accounts for 85%.
After ball milling 2 hours, compound is taken out, and ethyl alcohol is evaporated.Gains are gradually heating and curing, temperature ladder
Degree be respectively as follows: 120 DEG C 60 minutes, 140 DEG C 60 minutes, 160 DEG C 30 minutes.
3. carbonization
Dried solid is heat-treated, N is passed through2As protection gas, then with 5 DEG C/min be warming up to 800 DEG C into
Row carbonization.Heat preservation was cooled to room temperature to arrive graphene/amorphous carbon-coated graphite cathode material after 2 hours.
Embodiment 2-6
Embodiment 2-6 and 1 distinctive points of embodiment are the compound stage of step 1, and graphene additional amount is respectively 0.1%,
0.5%, 2%, 3%, 5%.
Embodiment 7
1. compound
Holy well phenolic resin PF9503, silane coupling agent 3- urea propyl-triethoxysilicane and graphene A are mixed.It will mix
Conjunction object is carried out uniformly mixed using high mixer.Wherein graphene A content is 1%, and silane contents are about 0.1%.Mixture is made
It is mediated with rheometer, is kept for 150 DEG C mix to balance, then take out cooling.
2. cladding
To be added hexamethylenetetramine in above-mentioned powder, hexamethylenetetramine additional amount by the practical hydroxyl value of phenolic resin into
Row calculates.Graphite powder is then added, graphite content in total system accounts for 90%.Mixture is subjected to mixed processing using high mixer
2 hours.After taking-up, mixture is gradually heating and curing, temperature gradient is respectively as follows: 130 DEG C 120 minutes, and 150 DEG C 60 points
Clock, 170 DEG C 30 minutes.
3. carbonization
Dried solid is heat-treated, N is passed through2As protection gas, then with 5 DEG C/min be warming up to 900 DEG C into
Row carbonization.Heat preservation was cooled to room temperature to arrive graphene/amorphous carbon-coated graphite cathode material after 2 hours.
Embodiment 8-10
The distinctive points of embodiment 8-10 and embodiment 7 are the cladding stage of step 2, and graphite content in total system is distinguished
Account for 93%, 95%, 97%.
Embodiment 11
1. compound
Thermoset urea aldehyde resin WPLQ-5115, silane coupling agent 3- urea propyl-triethoxysilicane and graphene A are mixed
It closes.Mixture is carried out using high mixer uniformly mixed.Wherein graphene A content is 1%, and coupling agent content is 0.5%.It will mix
It closes object to be mediated using rheometer, is kept for 150 DEG C mix to balance, then take out cooling.
2. cladding
Zinc sulfate (can also be substituted with diethy-aceto oxalate) will be added in above-mentioned powder, which presses Lauxite
Actual amount is calculated.Graphite powder is then added, graphite solid content in total system accounts for 95%.By mixture using high mixer into
Row mixed processing 2 hours.After taking-up, mixture is gradually heating and curing, temperature gradient is respectively as follows: 130 DEG C 120 minutes,
150 DEG C 60 minutes, 170 DEG C 30 minutes.
3. carbonization
Dried solid is heat-treated, N is passed through2As protection gas, then with 5 DEG C/min be warming up to 900 DEG C into
Row carbonization.Heat preservation was cooled to room temperature to arrive graphene/amorphous carbon-coated graphite cathode material after 2 hours.
Embodiment 12
1. compound
Holy well furane resins SH263, silane coupling agent 3- urea propyl-triethoxysilicane and graphene A are mixed.It will mix
Conjunction object is carried out uniformly mixed using high mixer.Wherein graphene A content is 1%, and coupling agent content is 0.3%.Mixture is made
It is mediated with rheometer, is kept for 150 DEG C mix to balance, then take out cooling.
2. cladding
Holy well furans curing agent GS05 will be added in above-mentioned powder, which is carried out by furane resins actual amount
It calculates.Graphite powder is then added, graphite solid content in total system accounts for 95%.Mixture is subjected to mixed processing using high mixer
2 hours.After taking-up, mixture is gradually heating and curing, temperature gradient is respectively as follows: 130 DEG C 120 minutes, and 150 DEG C 60 points
Clock, 170 DEG C 30 minutes.
3. carbonization
Dried solid is heat-treated, N is passed through2As protection gas, then with 5 DEG C/min be warming up to 900 DEG C into
Row carbonization.Heat preservation was cooled to room temperature to arrive graphene/amorphous carbon-coated graphite cathode material after 2 hours.
Embodiment 13
1. compound
By high molecular weight holy well epoxy resin SQPN-631, silane coupling agent 3- urea propyl-triethoxysilicane and graphene
A mixing.Mixture is carried out using high mixer uniformly mixed.Wherein graphene A content is 1%, and coupling agent content is 0.3%.
Mixture is mediated using rheometer, is kept for 150 DEG C mix to balance, then takes out cooling.
2. cladding
Diethylenetriamines (can also be substituted with ethylenediamine) will be added in above-mentioned powder, which presses asphalt mixtures modified by epoxy resin
The practical hydroxyl value of rouge is calculated.Graphite powder is then added, graphite solid content in total system accounts for 95%.Mixture is used high
Mixed machine carries out mixed processing 2 hours.After taking-up, mixture is gradually heating and curing, temperature gradient is respectively as follows: 130 DEG C 120
Minute, 150 DEG C 60 minutes, 170 DEG C 30 minutes.
3. carbonization
Dried solid is heat-treated, N is passed through2As protection gas, then with 5 DEG C/min be warming up to 900 DEG C into
Row carbonization.Heat preservation was cooled to room temperature to arrive graphene/amorphous carbon-coated graphite cathode material after 2 hours.
Embodiment 14
1. compound
Thermosetting epoxy asphalt hc-225, silane coupling agent 3- urea propyl-triethoxysilicane and graphene C are mixed.It will
Mixture is carried out uniformly mixed using high mixer.Wherein graphene A content is 1%, and coupling agent content is 0.3%.By mixture
It is mediated using rheometer, is kept for 150 DEG C mix to balance, then take out cooling.
2. cladding
By graphite powder in above-mentioned powder, graphite solid content in total system accounts for 95%.Mixture is carried out using high mixer
Mixed processing 2 hours.
3. carbonization
The solid mixed is heat-treated, N is passed through2As protection gas, then with 5 DEG C/min be warming up to 900 DEG C into
Row carbonization.Heat preservation was cooled to room temperature to arrive graphene/amorphous carbon-coated graphite cathode material after 2 hours.
Embodiment 15-16
Compared with Example 7, embodiment 15-16 distinctive points are graphene A replacing with graphene B and graphene respectively
C。
Control group:
According to a kind of patent publication No. CN104934603A " system of graphene doping and coated modified carbon graphite cathode material
Preparation Method " in embodiment 2 operated, obtained experimental result 1 data of table as above.
Experiment
The quality of above embodiments products obtained therefrom is tested, and is compared with control group, experimental method is the same as in CN104934603A
Embodiment 2, as a result such as table 1.
1 product quality of table
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (6)
1. a kind of preparation method of negative electrode material, characterized in that it comprises the following steps:
Covering is heated into kneading, cooling, graphite mixing is added, by being carbonized to obtain the final product；
The covering includes graphene, water-insoluble carbon matrix precursor and dispersing agent；The dispersing agent is three second of 3- urea propyl
Oxysilane；The carbon matrix precursor is one of phenolic resin, Lauxite, furane resins, epoxy resin, pitch or more
Kind；By weight, the graphene accounts for the 0.1-5% of the covering total amount, and the dispersing agent accounts for the covering total amount
0.05-0.1%；
When the carbon matrix precursor needs to solidify, it is additionally added curing agent after cooling and carries out curing reaction；
The curing agent is in hexamethylenetetramine, 3- diethyl amino propylamine, trimethylhexamethylenediamine, dihexyl triamine
It is one or more.
2. the preparation method of negative electrode material according to claim 1, which is characterized in that the covering, the graphite
Mass ratio is 3-15:85-97.
3. the preparation method of negative electrode material according to claim 2, which is characterized in that the covering, the graphite
Mass ratio is 5-10:90-95.
4. the preparation method of negative electrode material according to claim 1, which is characterized in that the carbonization is at 900 DEG C -1200
It is carried out at DEG C.
5. a kind of negative electrode material, which is characterized in that be prepared using the described in any item methods of Claims 1-4.
6. a kind of lithium ion battery, which is characterized in that the main cathode as described in claim 5 of the cathode of the lithium ion battery
Material is made.
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| CN201610231149.XA CN106469814B (en) | 2016-04-14 | 2016-04-14 | A kind of covering, negative electrode material, lithium ion battery and preparation method thereof |
| PCT/CN2017/080594 WO2017177970A1 (en) | 2016-04-14 | 2017-04-14 | Coating agent, negative electrode material, lithium ion battery, and preparation method therefor |
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| CN106469814B (en) * | 2016-04-14 | 2019-11-29 | 山东圣泉新能源科技有限公司 | A kind of covering, negative electrode material, lithium ion battery and preparation method thereof |
| CN109232985B (en) * | 2018-08-17 | 2021-01-05 | 广西大学 | Graphene material for asphalt modification and preparation method and application thereof |
| CN110854371A (en) * | 2019-11-26 | 2020-02-28 | 宁夏百川新材料有限公司 | Carbon composite negative electrode material and preparation method thereof |
| CN112787042B (en) * | 2020-04-24 | 2022-08-26 | 刘桥 | Lithium battery diaphragm and preparation method thereof |
| CN112537766A (en) * | 2020-11-17 | 2021-03-23 | 浙江大学自贡创新中心 | Preparation method of carbon-nitrogen composite negative electrode material for lithium ion battery |
| CN114551803A (en) * | 2022-02-26 | 2022-05-27 | 宁德新能源科技有限公司 | Three-dimensional gradient electrode for lithium metal cathode and preparation method thereof |
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