CN106469814A - A kind of covering, negative material, lithium ion battery and preparation method thereof - Google Patents
A kind of covering, negative material, lithium ion battery and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention provides a kind of covering, negative material, lithium ion battery and preparation method thereof.Covering includes：Graphene, non-water-soluble carbon matrix precursor, dispersant；Described dispersant is one or more of amino silane, epoxy radicals silicone hydride, polyvinyl alcohol.Negative material is mainly made up of graphite and this covering.Micro- capacitor theory that the covering of the present invention is mainly constituted using Graphene and amorphous carbon, greatly improves capacitance and the cycle-index of lithium ion battery.
Description
Technical field
The present invention relates to electrode material technical field, especially relate to a kind of covering, negative material,
Lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery refers to the general name with Lithium-ion embeding compound for positive electrode battery, and it is to contain
The compound of lithium makees positive pole, there is no lithium metal, only lithium ion.The discharge and recharge of lithium ion battery
Process is it is simply that the embedded and deintercalation process of lithium ion.During the embedded of lithium ion and deintercalation, with
When along with the embedded of lithium ion equivalent electronics and deintercalation.
For lithium ion battery negative, graphite is a kind of ideal material.Graphite has good
Good electric conductivity, degree of crystallinity is high, low cost, and bulk density is high, and theoretical embedding lithium capacity is high, is current
The pith of lithium ion battery negative material.But, itself there are disadvantages that, such as with electrolysis liquid phase
Capacitive is poor, and first charge-discharge reversible capacity is low, is not suitable for high current charge-discharge, and cycle performance is poor.
In order to solve the disadvantages mentioned above of graphite material, people are modified to graphite by various methods.
Common method of modifying is to be mixed into negative pole material using carbon matrix precursors such as Colophonium, resins as coating or covering
In material, then through carbonization.Through modified above, the capacitance of graphite cathode, cycle-index all have
Improved, but improved not notable, market significance is little.
Content of the invention
The first object of the present invention is to provide a kind of covering, and described covering can efficiently improve
The capacitance of lithium ion battery negative and cycle-index.
The second object of the present invention is to provide a kind of negative material, and described negative material has electric capacity
Amount is high, and cycle-index is many, steady performance.
The third object of the present invention is to provide a kind of preparation method of negative material, described preparation side
Method has multiple, is respectively provided with the advantages of flow process is simple, controllability is strong, production efficiency is high.
The fourth object of the present invention is to provide a kind of lithium ion battery, and described battery has capacitance
Height, cycle-index is many, steady performance, has broader practice prospect.
In order to solve above technical problem, the invention provides technical scheme below：
A kind of covering, including：Graphene, non-water-soluble carbon matrix precursor, dispersant；Described point
Powder is one or more of amino silane, epoxy radicals silicone hydride, polyvinyl alcohol.
This covering is mainly used in the negative pole modification to lithium ion battery, also be likely used for other unknown
Field.
Compared with material modified with existing lithium ion battery negative, this covering is mainly the increase in dispersion
Agent, to solve the scattering problem of Graphene and carbon matrix precursor, thus further increase electrode material
Capacity and cycle-index.
Wherein, carbon matrix precursor is extremely important to modified effect with the consistency problem of dispersant, the present invention
Select non-water-soluble carbon matrix precursor, and amino silane of arranging in pairs or groups, epoxy radicals silicone hydride, polyvinyl alcohol etc.
Dispersant, solves the problems referred to above.
Through statistics, compared with the modifying agent being not added with dispersant, the present invention is used for the negative of lithium ion battery
During pole, irreversible capacity reduces more than 5%；Compared with the graphite cathode being not added with any modifying agent, no
Reversible capacity reduces more than 10%, and cycle life and stability improve more than 30%.
Graphene of the present invention includes graphene nano lamella and Graphene, further includes biology
Matter graphene nano lamella and biomass Graphene.
Graphene of the present invention can be obtained by different preparation methoies, such as mechanical stripping method, outer
Epitaxial growth, chemical vapor infiltration, graphite oxidation reducing process, can also be by providing to biomass
Source hydrothermal carbonization method, and the Graphene that in prior art prepared by other methods.But, some methods
It is difficult to realize and prepare the theoretic Graphene of stricti jurise, for example a part of prior art on a large scale
Can there is some impurity elements, other allotropes of carbon or layer in the Graphene preparing
The graphene-structured (such as 3 layers, 5 layers, 10 layers, 20 layers etc.) of the non-monolayers of number or even multilamellar, this
Bright using Graphene also include the Graphene on above-mentioned non-critical theory of meaning.
Graphene nano lamella can adopt Jinan holy well company technique, with agriculture and forestry organic waste material as primary raw material,
Obtain the multiporous biological matter with excellent conductive property by steps such as hydrolysis, catalytic treatment, heat treatments
Graphene complex, its be mainly characterized by the contained Graphene number of plies be 1～10 layer between, non-carbon non-oxygen
Constituent content is 0.5wt%～6wt%.
Above-mentioned covering can also improve further：
Further, described carbon matrix precursor is preferably phenolic resin, Lauxite, furane resins, ring
One or more of oxygen tree fat, Colophonium.
The impalpable structure that above carbon matrix precursor is formed after carbonization enriches, and is more beneficial for lithium ion
Embed and deintercalation, decrease the consumption of lithium ion when forming SEI film during initial charge.Specifically,
Above resin selects thermosetting resin, the resin of high molecular in selecting further further, and Colophonium is excellent
Select thermoset pitch.
Further, by weight, described Graphene accounts for the 0.1-5% of covering total amount, preferably
0.5-3%, further preferred 1-2%；Described dispersant accounts for the 0.05-0.5% of covering total amount, preferably
0.05-0.3%, further preferred 0.05-0.1%.
The proportioning of each raw material has a major impact to modified effect, when being mixed with aforementioned proportion, is uniformly dispersed,
And carbonization effect is good, more conducively improve capacity and the life-span of battery.
Further, also include the firming agent for described carbon matrix precursor.
Firming agent is added to be conducive to the setting of described carbon matrix precursor, the type of firming agent and consumption according to carbon
Selecting, such as, when carbon matrix precursor is for thermosetting resin, available firming agent has six first to presoma
Urotropine, 3- diethyl amino propylamine, trimethylhexamethylenediamine, dihexyl triamine etc..
Further, in dispersant, amino silane, epoxy radicals silicone hydride refer to respectively containing amino or epoxy
Any silane of base, such as epoxy radicals trimethoxysilane coupling agent etc..It is silane coupler further
3- urea propyl-triethoxysilicane etc..
In addition, the present invention provides a kind of negative material, mainly by graphite and covering system mentioned above
Become.
This negative material then coordinates the covering of the present invention using conventional graphite as active material,
Than traditional negative material, will there is higher capacitance and cycle-index.Equally, this negative pole material at present
Material is mainly used in lithium ion battery, but is also possible to the battery for other UNKNOWN TYPEs.When for lithium
During ion battery, available positive electrode has LiMn2O4, cobalt acid lithium or LiFePO4 etc..
Above negative material can improve further, for example：
Further, by weight, described covering, the proportioning of described graphite are 3-15:85-97.
Comparatively, the negative pole of above ratio can give full play to the modified effect of the covering of the present invention,
Preferably 5-10:90-95, further 5-8:90-93.If certainly consider cost, potential etc. other because
When plain, it would however also be possible to employ the proportioning outside scope.
In addition, covering of the present invention can each raw material independent packaging, now with existing mixed；Can also
Directly mix storage, depending on this mainly requires according to storage, transport etc..When being mixed with graphite
During negative material, can one of in the following ways：
Mode one：By described Graphene, described carbon matrix precursor, described dispersant, described graphite molten
Dissolve in agent and mix, be dried afterwards, carbonization obtains final product；
Mode two：Described Graphene, described carbon matrix precursor, described dispersant are dissolved simultaneously in a solvent
Mix, mix with graphite after drying, recarbonize and obtain final product；
Wherein, when containing described firming agent in described covering, described mode one and described mode two
Middle it is additionally added described firming agent when described Graphene is dissolved in a solvent, and before described carbonization
Also carry out curing reaction.
Both the above mode broadly falls into solwution method, and both differences are that the opportunity that is dried is different, that is, be both dried
Can carry out can also carrying out after adding graphite before adding graphite.The advantage of both modes is institute
Equipment is simple, and key point is to mix step, to ensure that each composition is uniformly dispersed mutually.Mixing side
Formula can adopt multiple, such as ball milling, ball milling and dissolving can carry out simultaneously, and Ball-milling Time is generally 1-4h,
It is defined by mixing.
Can be to stir in charging or dissolve respectively, then during dissolving and mixing
Mixing together.
Drying meanss have many kinds, and typically depending on the type of solvent, available method has heating evaporation
Deng.
When containing firming agent, the opportunity of curing reaction is before carburizing reagent, and in mode one
In both can after drying or mix after and be dried before；Both permissible in mode two
Before admixed graphite it is also possible to after drying or after admixed graphite and before drying.
In addition, above-mentioned negative material also can adopt following preparation method：
By described Graphene, described carbon matrix precursor, described dispersant heating kneading, cooling, add
Described graphite mixing, obtains final product through carbonization；
When containing described firming agent in described covering, after described cooling, it is additionally added described solidification
Agent, and also carry out curing reaction before described carbonization.
The method belongs to fusion method, and its advantage is that production efficiency is high.Its described kneading can adopt multiple
Equipment, such as flow graph etc..Preferably all raw materials are pre-mixed before described kneading.
Described kneading condition is further：Mixed to balance at 150 DEG C with flow graph.
Carbonization of the present invention is further：Carry out at 900 DEG C -1200 DEG C.
Depending on curing reaction of the present invention is mainly according to firming agent and resinous type, usually gradient
It is heating and curing, condition of cure is taking phenolic resin as a example：120-130 DEG C 60 minutes,
140-150 DEG C 60 minutes, 160-170 DEG C 30 minutes.
In addition to three kinds of preparation methoies provided above, negative material of the present invention may also be employed other
Preparation method.
Present invention also offers a kind of lithium ion battery, the negative pole of described lithium ion battery is mainly by above
Described negative material is made.
Described above, this lithium ion battery has higher electric capacity than traditional lithium ion battery
Amount, more cycle-indexes, longer service life, more stable storage performance.
Compared with prior art, the present invention has following technique effect：
(1) dispersion effect of covering is good, can more improve electrode material capacitance,
The performances such as life-span, stability.
(2) provide capacitance high, cycle-index is many, the negative material of stable performance and battery.
(3) provide the multiple methods preparing negative material, be that Producer provides more more options.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is clearly and completely described,
It will be appreciated by those skilled in the art that following described embodiment is a present invention part implementing
Example, rather than whole embodiments, are merely to illustrate the present invention, and are not construed as limiting the present invention's
Scope.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creative labor
The every other embodiment being obtained under the premise of dynamic, broadly falls into the scope of protection of the invention.In embodiment
Unreceipted actual conditions person, the condition according to normal condition or manufacturer's suggestion is carried out.Agents useful for same or
The unreceipted production firm person of instrument, being can be by the commercially available conventional products bought and obtain.
Prepare Graphene A：
First prepare cellulose：
(1) by after wheat straw comminution pretreatment, using the dense formic acid for 80wt% of total acid and acetic acid
Organic acid solution carries out steaming and decocting to the wheat straw after processing, acetic acid and first in the organic acid solution of the present embodiment
The mass ratio of acid is 1:12, and add the hydrogen peroxide accounting for wheat straw raw material 1wt% before adding raw material
(H2O2) as catalyst, 120 DEG C of controlling reaction temperature, react 30min, solid-liquid mass ratio is 1:10,
And the reactant liquor obtaining is carried out first time solid-liquid separation；
(2) solid that first time solid-liquid separation obtains is added the dense formic acid for 75wt% of total acid and acetic acid
Organic acid solution carry out acid elution, wherein above-mentioned total acid dense for add in the organic acid solution of 75wt% account for little
Hydrogen peroxide (the H of wheat straw raw material 8wt%2O2) as catalyst and acetic acid with the mass ratio of formic acid is
1:12, control temperature to be 90 DEG C, wash time 1h, solid-liquid mass ratio is 1:9, and reactant liquor is entered
Second solid-liquid separation of row；
(3) collect for the first time and the liquid that obtains of second solid-liquid separation, in 120 DEG C, under 301kPa
Carry out High Temperature High Pressure evaporation, until being evaporated, by the formic acid obtaining and acetic acid vapor condensing reflux to step
(1) as cooking liquor in reactor, for the steaming and decocting of step (1)；
(4) solid that second solid-liquid separation of collection obtains, and washed, control washing temperature is
80 DEG C, washing slurry dense for 6wt%, and the washing slurry obtaining is carried out third time solid-liquid separation；
(5) collect the liquid that third time solid-liquid separation obtains, carry out water, sour rectification, the mixing obtaining
Acid solution is back to the steaming and decocting being used for step (1) in the reactor of step (1) as cooking liquor, obtains
Water circulation wash water with water in step (5)；
(6) collect the solid that obtains of third time solid-liquid separation and carry out screening and obtain required screened stock fiber
Element.
Then Graphene is prepared for raw material with the cellulose being prepared as above：
(1) in mass ratio 1:1 cellulose mixture and ferrous chloride, stir at 150 DEG C and are catalyzed
Process 4h, be dried to presoma moisture 10wt%, obtain presoma；
(2)N2In atmosphere, with 3 DEG C/min speed, presoma is warming up to 170 DEG C, is incubated 2h, it
Temperature programming, to 400 DEG C, is incubated 3h, is warming up to 1200 DEG C afterwards afterwards, obtains crude product after insulation 3h；
The heating rate that described program heats up is 15 DEG C/min；
(3) at 55-65 DEG C, by crude product be 10% through over-richness sodium hydroxide solution, 4wt% hydrochloric acid
After pickling, washing obtains biomass Graphene, is designated as Graphene A.
Prepare Graphene B：
Using the method for embodiment in the patent of Publication No. CN104724696A 10, specially：Receive
Collection straw, shreds into small pieces after processing totally, is immersed in ethanol solution, with the rotating speed of 100r/min
At the uniform velocity stir 5 hours；Then solution is transferred in high speed centrifuge, rotating speed is set to 3000r/min,
Centrifugation time is 20 minutes, takes off the broken sample of layer after terminating.Under normal temperature and pressure, broken sample is loaded a diameter of
In the Tissue Culture Dish of 15cm, it is placed in air inlet, adjusts flow parameter, setting wind speed is 6m/s,
Air quantity is 1400m3/ h, keeps ventilation state 12 hours；Tube furnace is warmed up to 1300 DEG C, is passed through inertia
Gas shield, keeps 30 minutes；Dried broken sample is positioned in tube furnace, heats 5 hours,
After being cooled to room temperature, obtain overburden ratio obvious biomass Graphene, be designated as Graphene B.
Prepare Graphene C：
Using the method for embodiment in the patent of Publication No. CN105217621A 1, specially：
(1) by 2g graphite powder and 3g potassium dithionate, 3g phosphorus pentoxide and 12mL in reactor
React in the mixed system of concentrated sulphuric acid, stir 4 hours under 80 DEG C of water bath condition, navy blue is molten to being formed
Liquid, cooling, sucking filtration, be dried after obtain pre-oxidize graphite；
(2) take the graphite oxide 2g obtained by step (1) in three-neck flask, in the bar of ice-water bath
With 150mL concentrated sulfuric acid solution under part, it is gradually added into the potassium permanganate of 25g, stir 2 hours；
(3) three-neck flask of above-mentioned steps (2) is proceeded to oil bath, be warming up to 35 DEG C, stirring 2 is little
When, continuation is stirred and is 1 according to volume ratio:15 amount adds 30wt% hydrogen peroxide and deionized water
Mixed solution；Sucking filtration, the dilute hydrochloric acid being 10% with 4mL mass fraction respectively and deionized water clean 1 time,
Centrifugation, obtains the graphene oxide aoxidizing for the first time after being dried；
(4) by the graphene oxide 2g of preparation in step (3) again under conditions of ice-water bath with 50mL
Concentrated sulfuric acid solution be mixed in three-neck flask, be gradually added into the KMnO of 8g4, stir 1 hour；
(5) three-neck flask of above-mentioned steps (4) is proceeded to oil bath, be warming up to 40 DEG C, stirring 1 is little
When, then proceed to be warming up to 90 DEG C, after stirring 1 hour, continuation is stirred and is 1 according to volume ratio:7
Amount add the mixed solution of 30wt% hydrogen peroxide and deionized water, cool down after continuing stirring 6 hours, take out
Filter, the dilute hydrochloric acid being 10% with 4mL mass fraction respectively and deionized water clean 2 times, centrifugation, are dried
Obtain the graphene oxide of size uniformity afterwards, be designated as Graphene C.
The following is embodiment percentage ratio to be all weight percentage.
Embodiment 1
1. it is combined
Holy well phenolic resin PF9503 is dissolved in ethanol, adds silane coupler 3- urea propyl group three second
TMOS and trimethylhexamethylenediamine.Mixture is carried out ball milling 2 hours.By Graphene A
Progressively it is dividedly in some parts in ball milling system, keep ball milling 2 hours.In final mixture, Graphene contains
Measure as 1%, silane contents are about 0.05%, and trimethylhexamethylenediamine addition is according to phenolic resin
Actual hydroxyl value is calculated.
2. coat
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, complex is taken out, and ethanol is evaporated.Gains are carried out progressively adding
Heat cure, thermograde is respectively:120 DEG C 60 minutes, 140 DEG C 60 minutes, 160 DEG C 30 points
Clock.
3. carbonization
Dried solid is carried out heat treatment, is passed through N2As shielding gas, then with 5 DEG C/min liter
Temperature carries out carbonization to 800 DEG C.Insulation was cooled to room temperature after 2 hours, that is, obtain Graphene/amorphous
The graphite cathode material of carbon coating.
Embodiment 2-6
Embodiment 2-6 and embodiment 1 distinctive points are the compound stage of step 1, Graphene addition
It is respectively 0.1%, 0.5%, 2%, 3%, 5%.
Embodiment 7
1. it is combined
By holy well phenolic resin PF9503, silane coupler 3- urea propyl-triethoxysilicane and Graphene
A mixes.Mixture is carried out mix homogeneously using high mixer.Wherein Graphene A content is 1%, silicon
Alkane content is about 0.1%.Mixture is mediated using flow graph, keeps 150 DEG C and mix to moment of torsion
Balance, subsequently takes out cooling.
2. coat
Hexamethylenetetramine will be added, it is real that hexamethylenetetramine addition presses phenolic resin in above-mentioned powder
Border hydroxyl value is calculated.It is subsequently added graphite powder, graphite content in total system accounts for 90%.To mix
Thing carries out mixed processing 2 hours using high mixer.After taking-up, mixture is progressively heating and curing,
Thermograde is respectively:130 DEG C 120 minutes, 150 DEG C 60 minutes, 170 DEG C 30 minutes.
3. carbonization
Dried solid is carried out heat treatment, is passed through N2As shielding gas, then with 5 DEG C/min liter
Temperature carries out carbonization to 900 DEG C.Insulation was cooled to room temperature after 2 hours, that is, obtain Graphene/amorphous
The graphite cathode material of carbon coating.
Embodiment 8-10
The distinctive points of embodiment 8-10 and embodiment 7 are the cladding stage of step 2, and graphite is overall
In system, content accounts for 93%, 95%, 97% respectively.
Embodiment 11
1. it is combined
By thermoset urea aldehyde resin WPLQ-5115, silane coupler 3- urea propyl-triethoxysilicane and
Graphene A mixes.Mixture is carried out mix homogeneously using high mixer.Wherein Graphene A content is
1%, being coupled agent content is 0.5%.Mixture is mediated using flow graph, is kept 150 DEG C of mixing
To balance, subsequently take out cooling.
2. coat
Zinc sulfate (also can be substituted), this firming agent addition will be added with ethyl oxalate in above-mentioned powder
Calculated by Lauxite actual amount.It is subsequently added graphite powder, graphite solid content in total system accounts for
95%.Mixture is carried out mixed processing 2 hours using high mixer.After taking-up, by mixture carry out by
Step is heating and curing, and thermograde is respectively:130 DEG C 120 minutes, 150 DEG C 60 minutes, 170 DEG C
30 minutes.
3. carbonization
Dried solid is carried out heat treatment, is passed through N2As shielding gas, then with 5 DEG C/min liter
Temperature carries out carbonization to 900 DEG C.Insulation was cooled to room temperature after 2 hours, that is, obtain Graphene/amorphous
The graphite cathode material of carbon coating.
Embodiment 12
1. it is combined
By holy well furane resins SH263, silane coupler 3- urea propyl-triethoxysilicane and Graphene A
Mixing.Mixture is carried out mix homogeneously using high mixer.Wherein Graphene A content is 1%, is coupled
Agent content is 0.3%.Mixture is mediated using flow graph, keeps 150 DEG C to mix and put down to moment of torsion
Weighing apparatus, subsequently takes out cooling.
2. coat
Holy well furan firming agent GS05 will be added, this firming agent addition presses furane resins in above-mentioned powder
Actual amount is calculated.It is subsequently added graphite powder, graphite solid content in total system accounts for 95%.To mix
Thing carries out mixed processing 2 hours using high mixer.After taking-up, mixture is progressively heating and curing,
Thermograde is respectively:130 DEG C 120 minutes, 150 DEG C 60 minutes, 170 DEG C 30 minutes.
3. carbonization
Dried solid is carried out heat treatment, is passed through N2As shielding gas, then with 5 DEG C/min liter
Temperature carries out carbonization to 900 DEG C.Insulation was cooled to room temperature after 2 hours, that is, obtain Graphene/amorphous
The graphite cathode material of carbon coating.
Embodiment 13
1. it is combined
By high molecular holy well epoxy resin SQPN-631, silane coupler 3- urea propyl-triethoxysilicane
Alkane and Graphene A mixing.Mixture is carried out mix homogeneously using high mixer.Wherein Graphene A contains
Measure as 1%, being coupled agent content is 0.3%.Mixture is mediated using flow graph, is kept 150 DEG C
Mix to balance, subsequently take out cooling.
2. coat
Diethylenetriamines (also can be substituted) will be added with ethylenediamine, this firming agent adds in above-mentioned powder
Amount is calculated by the actual hydroxyl value of epoxy resin.It is subsequently added graphite powder, graphite is solid in total system
Content accounts for 95%.Mixture is carried out mixed processing 2 hours using high mixer.After taking-up, by mixture
Progressively it is heating and curing, thermograde is respectively:130 DEG C 120 minutes, 150 DEG C 60 minutes,
170 DEG C 30 minutes.
3. carbonization
Dried solid is carried out heat treatment, is passed through N2As shielding gas, then with 5 DEG C/min liter
Temperature carries out carbonization to 900 DEG C.Insulation was cooled to room temperature after 2 hours, that is, obtain Graphene/amorphous
The graphite cathode material of carbon coating.
Embodiment 14
1. it is combined
By thermosetting epoxy asphalt hc-225, silane coupler 3- urea propyl-triethoxysilicane and graphite
Alkene C mixes.Mixture is carried out mix homogeneously using high mixer.Wherein Graphene A content is 1%,
Being coupled agent content is 0.3%.Mixture is mediated using flow graph, keeps 150 DEG C and mix to torsion
Square balances, and subsequently takes out cooling.
2. coat
By graphite powder in above-mentioned powder, graphite solid content in total system accounts for 95%.By mixture using high
Mixed machine carries out mixed processing 2 hours.
3. carbonization
The solid mixing is carried out heat treatment, is passed through N2As shielding gas, then with 5 DEG C/min liter
Temperature carries out carbonization to 900 DEG C.Insulation was cooled to room temperature after 2 hours, that is, obtain Graphene/amorphous
The graphite cathode material of carbon coating.
Embodiment 15-16
Compared with Example 7, embodiment 15-16 distinctive points are for Graphene A to replace with stone respectively
Black alkene B and Graphene C.
Matched group：
According to patent publication No. CN104934603A《A kind of Graphene doping is born with coated modified carbon graphite
The preparation method of pole material》In embodiment 2 operated, the experimental result obtaining for example upper table 1 number
According to.
Experiment
The quality of test above example products obtained therefrom, and contrast with matched group, experimental technique is same
Embodiment 2 in CN104934603A, result such as table 1.
Table 1 product quality
Finally it should be noted that：Various embodiments above only in order to technical scheme to be described, rather than
It is limited；Although being described in detail to the present invention with reference to foregoing embodiments, this area
Those of ordinary skill should be understood：It still can enter to the technical scheme described in foregoing embodiments
Row modification, or equivalent is carried out to wherein some or all of technical characteristic；And these modification or
Person replaces, and does not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a kind of covering is it is characterised in that include：Graphene, non-water-soluble carbon matrix precursor,
And dispersant；Described dispersant is one of amino silane, epoxy radicals silicone hydride, polyvinyl alcohol or many
Kind.
2. covering according to claim 1 is it is characterised in that described carbon matrix precursor is phenolic aldehyde
One or more of resin, Lauxite, furane resins, epoxy resin, Colophonium.
3. covering according to claim 1 it is characterised in that by weight, described graphite
Alkene accounts for the 0.1-5% of described covering total amount, and described dispersant accounts for described covering total amount
0.05-0.1%.
4. the covering according to any one of claim 1-3 is it is characterised in that described covering
Also include the firming agent for described carbon matrix precursor；Preferably, described firming agent is selected from six methines four
One or more of amine, 3- diethyl amino propylamine, trimethylhexamethylenediamine, dihexyl triamine.
5. a kind of negative material it is characterised in that main by graphite and any one of claim 1-4 institute
The covering stated is made.
6. negative material according to claim 5 is it is characterised in that described covering, described
The mass ratio of graphite is 3-15:85-97, preferably 5-10:90-95.
7. the negative material described in claim 5 or 6 preparation method it is characterised in that adopt with
One of under type：
Mode one：By described Graphene, described carbon matrix precursor, described dispersant, described graphite molten
Dissolve in agent and mix, be dried afterwards, carbonization obtains final product；
Mode two：Described Graphene, described carbon matrix precursor, described dispersant are dissolved simultaneously in a solvent
Mix, mix with graphite after drying, recarbonize and obtain final product；
Wherein, when containing described firming agent in described covering, described mode one and described mode two
Middle it is additionally added described firming agent when described Graphene is dissolved in a solvent, and before described carbonization
Also carry out curing reaction.
8. under the preparation method of the negative material described in claim 5 or 6 is it is characterised in that include
Row step：
By described Graphene, described carbon matrix precursor, described dispersant heating kneading, cooling, add
Described graphite mixing, obtains final product through carbonization；
When containing described firming agent in described covering, after described cooling, it is additionally added described solidification
Agent, and also carry out curing reaction before described carbonization.
9. the preparation method of the negative material according to claim 7 or 8 is it is characterised in that institute
Stating carbonization is to carry out at 900 DEG C -1200 DEG C.
10. a kind of lithium ion battery is it is characterised in that the negative pole of described lithium ion battery is mainly by right
The negative material described in 5 or 6 is required to make.
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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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| CN201610231149.XA CN106469814B (en) | 2016-04-14 | 2016-04-14 | A kind of covering, negative electrode material, lithium ion battery and preparation method thereof |
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| WO2017177970A1 (en) * | 2016-04-14 | 2017-10-19 | 济南圣泉集团股份有限公司 | Coating agent, negative electrode material, lithium ion battery, and preparation method therefor |
| 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 |
| CN114551830A (en) * | 2022-02-21 | 2022-05-27 | 海城申合科技有限公司 | Preparation method of graphene oxide coated artificial graphite lithium ion negative electrode material |
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| CN109232985B (en) * | 2018-08-17 | 2021-01-05 | 广西大学 | Graphene material for asphalt modification and preparation method and application 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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Also Published As
| Publication number | Publication date |
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| CN106469814B (en) | 2019-11-29 |
| WO2017177970A1 (en) | 2017-10-19 |
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