CN108075112A - Negative electrode material for lithium ion battery and method for producing same - Google Patents
Negative electrode material for lithium ion battery and method for producing same Download PDFInfo
- Publication number
- CN108075112A CN108075112A CN201710076350.XA CN201710076350A CN108075112A CN 108075112 A CN108075112 A CN 108075112A CN 201710076350 A CN201710076350 A CN 201710076350A CN 108075112 A CN108075112 A CN 108075112A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- negative electrode
- cathode material
- chitin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 82
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 229920002101 Chitin Polymers 0.000 claims abstract description 70
- 230000004048 modification Effects 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 54
- 239000010406 cathode material Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- -1 Delanium Inorganic materials 0.000 claims description 30
- 239000002482 conductive additive Substances 0.000 claims description 25
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910001339 C alloy Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910021483 silicon-carbon alloy Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000006232 furnace black Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229940125717 barbiturate Drugs 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 11
- 239000013543 active substance Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 21
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KCFTYNYWGLBFSZ-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound COC(CC)O.COC(CC)O KCFTYNYWGLBFSZ-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a negative electrode material for a lithium ion battery and a manufacturing method thereof. The manufacturing method of the negative electrode material for the lithium ion battery comprises the steps of preparing a sulfonated chitin aqueous solution and carrying out surface modification on a negative electrode active substance by using the sulfonated chitin aqueous solution. The negative electrode material for the lithium ion battery comprises a negative electrode active substance, and the surface of the negative electrode active substance is provided with a modification layer containing sulfonated chitin. According to the method for manufacturing the negative electrode material for the lithium ion battery, sulfonated chitin can be modified on the surface of the negative electrode active substance at normal temperature. According to the negative electrode material for the lithium ion battery, the effect of the propylene carbonate electrolyte resistance of the negative electrode material can be improved.
Description
Technical field
The present invention relates to a kind of manufacturing method of negative material, and more particularly to a kind of cathode material of lithium ion battery and
Its manufacturing method.
Background technology
Lithium ion battery is one of most common type of rechargeable battery in portable electronic device, close with high-energy
It spends, memory-less effect, when not in use only slow loss of charge.
And in the manufacturing method of existing cathode material of lithium ion battery, it need to usually pass through high-temperature heat treatment repeatedly
Process, energy loss are more and time-consuming.
On the other hand, it is known that adding propene carbonate (propylene carbonate, PC) in battery electrolyte can change
Kind performance of the lithium ion battery in low-temperature operation.However, because negative material is bad to the tolerance of propene carbonate, therefore
The additive amount of propene carbonate is restricted at present, is at most only capable of being added to 10%, spy, which is traced it to its cause, to be：Lithium-ion electric at present
Most commonly used or graphite type material such as native graphite in the negative material of pond, and propylene carbonate solvent can not be in these graphite
Class electrode surface forms effectively passivating film, and easily as lithium ion is embedded in graphite linings jointly, graphite electrode structure is caused brokenly
It is bad, cause battery reversible capacity low, poor circulation seriously affects battery performance.
In view of this, it is desirable that a kind of manufacturing method of cathode material of lithium ion battery that can be solved the above problems and
Cathode material of lithium ion battery.
The content of the invention
The present invention provides a kind of manufacturing method of cathode material of lithium ion battery, can complete surface at normal temperatures and repair
Decorations make obtained negative material have the excellent electrolyte of resistance to propene carbonate effect.
The present invention separately provides a kind of cathode material of lithium ion battery, can promote the resistance to propene carbonate electricity of negative material
Solve the effect of liquid.
The manufacturing method of the cathode material of lithium ion battery of the present invention comprises the following steps：Prepare monosulfonic acid chitin
Aqueous solution and negative electrode active material is surface modified using sulfonated chitin water soluble liquid.
In one embodiment of this invention, before being surface modified, it is additionally included in sulfonated chitin water soluble liquid
Hybrid conductive additive.
The cathode material of lithium ion battery of the present invention includes the surface tool of negative electrode active material, wherein negative electrode active material
There is the decorative layer containing sulfonated chitin.
In another embodiment of the invention, cathode material of lithium ion battery further includes conductive additive.
In another embodiment of the invention, conductive additive can be carbon black, acetylene black, carbon nanotubes, conductive carbon fibre,
Graphene, furnace black, Delanium, aquadag, copper powder, zinc powder, nickel powder, silver powder or its combination.
In another embodiment of the invention, negative electrode active material may be selected from least one in the group being made up of
Kind：Native graphite, Delanium, carbon alloy, surface metal modification carbon material, metatitanic acid salt, silicon, silica and silicon-carbon alloy.
In various embodiments of the present invention, the weight composition ratio of conductive additive p-sulfonic acid chitin is smaller than
In 5.
In various embodiments of the present invention, the weight composition ratio of conductive additive p-sulfonic acid chitin is smaller than
In 2.5.
In various embodiments of the present invention, the weight average molecular weight of sulfonated chitin can between 2,000~1,
Between 000,000.
In various embodiments of the present invention, compared with the full dose of negative electrode active material, the modification amount of sulfonated chitin
Can be 0.05%~20%.
In various embodiments of the present invention, compared with the full dose of negative electrode active material, the modification amount of sulfonated chitin
Can be 0.15%~10%.
It, can at normal temperatures, by sulphur by the manufacturing method of the cathode material of lithium ion battery of the present invention based on above-mentioned
Chitosan-modified is acidified on the surface of negative electrode active material so that cathode material of lithium ion battery has excellent resistance to carbonic acid third
Enester electrolyte effect.
To make the foregoing features and advantages of the present invention clearer and more comprehensible, special embodiment below, and attached drawing shown in cooperation
It is described in detail below.
Description of the drawings
Fig. 1 is a kind of manufacturing process block diagram of cathode material of lithium ion battery according to one embodiment of the invention；
Fig. 2 is a kind of diagrammatic cross-section of cathode material of lithium ion battery according to another embodiment of the present invention；
Fig. 3 A are the SEM figures of the negative material of comparative example 1；
Fig. 3 B are the SEM figures that Fig. 3 A amplify 10 times；
Fig. 4 A are the SEM figures of the negative material of experimental example 1；
Fig. 4 B are the SEM figures that Fig. 4 A amplify 10 times；
Fig. 5 A be experimental example 1 negative material concentration be 33% propene carbonate electrolyte under, with 0.1C be melted into three
SEM figures after circle；
Fig. 5 B are the SEM figures that Fig. 5 A amplify 4 times；
Fig. 6 A be comparative example 1 negative material concentration be 33% propene carbonate electrolyte under, with 0.1C be melted into three
SEM figures after circle；
Fig. 6 B are the SEM figures that Fig. 6 A amplify 4 times；
Fig. 7 is the lithium-ion electric being mixed by the negative material of experimental example 1 and the electrolyte of high carbon acid propylene ester concentration
The charge/discharge graph in pond；
Fig. 8 is the lithium-ion electric being mixed by the negative material of comparative example 1 and the electrolyte of high carbon acid propylene ester concentration
The charge/discharge graph in pond；
Fig. 9 is that electrolyte of experimental example 1 and comparative example 1 the negative material respectively with high carbon acid propylene ester concentration mixes system
Into lithium ion battery charge/discharge cycle graph；
Figure 10 be comparative example 2,2~experimental example of experimental example 5 negative material water contact angle change curve；
Figure 11 is the lithium-ion electric being mixed by the negative material of embodiment 6 and the electrolyte of high carbon acid propylene ester concentration
The charge/discharge graph in pond；
Figure 12 is the lithium-ion electric being mixed by the negative material of embodiment 6 and the electrolyte of high carbon acid propylene ester concentration
The charge/discharge cycle graph in pond.
Reference sign：
100、102：Step
200：Cathode material of lithium ion battery
202：Negative electrode active material
204：Decorative layer
Specific embodiment
Fig. 1 is a kind of manufacturing process block diagram of cathode material of lithium ion battery according to one embodiment of the invention.
With reference to Fig. 1, step 100 is carried out first, monosulfonic acid chitin water soluble liquid is prepared, and prepares sulfonated chitin water
Any known mode that sulfonated chitin can be dissolved in water can be used in the mode of solution.Detailed content will be in being described below.
Then, step 102 is carried out, negative electrode active material is surface modified using sulfonated chitin water soluble liquid,
Middle negative electrode active material is for example selected from least one of group being made up of：Native graphite, Delanium, carbon alloy,
Surface metal modification carbon material, metatitanic acid salt, silicon, silica and silicon-carbon alloy.Specifically, can be at 20 DEG C to 40 DEG C it is normal
Under temperature, negative electrode active material is surface modified, and optionally, can also in sulfonated chitin water soluble liquid hybrid conductive
Add agent.For the preferable viewpoint of mixing uniformity, preferably before being surface modified, in sulfonated chitin water soluble liquid
First hybrid conductive additive, in the case, the larger conductive additive of surface area may be homogenously dispersed in sulfonated chitin water
In solution, easily make sulfonated chitosan-modified on negative electrode active material surface, and help uniformly to adhere to conductive additive
On negative electrode active material surface.In addition, the temperature of hybrid conductive additive can be 20 DEG C to 40 DEG C, but not limited to this.Therefore, originally
The method of embodiment whole can at normal temperatures carry out, and manufacturing process does not take simply.
Before step 100, sulfonated chitin can be prepared for example by following manner.First, under a proper temperature
And in the presence of organic solvent, come using hydrocarbyl sultone compound compound (hydrocarbyl sultone compound)
The sulfonated chitin (chitin) not modified with amino functional group (amino functional groups), and make
It obtains in the molecular structure of the chitin through chemical modification, has the amino functional group of predetermined ratio via covalent bond
(covalent bond) and given by hydrocarbyl sultone compound compound sulfonated.Wherein, organic solvent can be with high-polarity
Solvent, organic solvent be, for example, be selected from by following formed group:Alcohol (alcohol), ether (ether), ether alcohol
(etheralcohol) and combinations thereof.In some embodiments, organic solvent is selected from by following formed group:Methanol,
Ethyl alcohol, isopropanol, butanol, methoxypropanol (methoxypropanol) and combinations thereof.In specific concrete example, You Jirong
Agent can have the water less than 10%.
The above-mentioned chitin not modified can be pretreated, to influence the result of sulfonated reaction.For example, do not modify
Chitin can amino functional group be allowed access to by deacetylation (deacetylated).The chitin not modified also may be used
To carry blocking group (protective group) to limit sulfonated degree, although this is not in many concrete examples
It needs.Reactive group can be provided that other related with hydrocarbyl sultone compound compound is promoted to be intended to react.
In addition, above-mentioned sulfonated reaction can be carried out for example under the reflux temperature of organic solvent used.Organic solvent
Reflux temperature can be between 50 DEG C to 150 DEG C and be more preferably between 60 DEG C to 140 DEG C.
Above-mentioned hydrocarbyl sultone compound compound includes but not limited to alkyl sultone (alkyl sultone) or alkenyl sultone
(alkenyl sultone).Hydrocarbyl sultone compound compound step by step or all can once be injected towards the crust by not modifying
In the mixture that element and organic solvent are formed.The hydrocarbyl sultone compound compound usually overwhelming majority is chitin with not modifying
Amino functional group reaction, and seldom or not with hydroxyl group react.Furthermore hydrocarbyl sultone compound compound is usually predominantly
Via covalent bond by the sulfonated amino functional group to the chitin not modified.
The weight average molecular weight of the sulfonated chitin of the present embodiment is for example between 2,000~1,000,000.Not
Modification and weight average molecular weight are, for example, 2400 chitin, although with water solubility, using its modification such as natural stone
During the surface of the negative electrode active material 202 of black (nature graphite, NG), native graphite still can not be effectively promoted to carbonic acid
The tolerance level of acrylic ester (propylene carbonate, PC) electrolyte.It is used that is, not having water-soluble chitin
In the modification i.e. effect with performance improvement of negative electrode active material, if chitin is also unable to reach the present invention's without sulfonated
Effect.
In a step 102, compared with the full dose of negative electrode active material, the modification amount of sulfonated chitin can be 0.05%~
20%, preferably 0.15%~10%.The definition of modification amount is:(the weight of weight/negative electrode active material of sulfonated chitin
Amount) × 100%.If modification amount is too low, then the hydrophily of sulfonated chitin is poor, is not easy to be distributed in water.If modification amount
Too much, then blocked up decorative layer is had on the surface of negative electrode active material to generate, and causes ion that can not enter internally positioned bear
Pole active material, capacitance decline, and negative material easily lumps in drying, can not become powder, although mechanical force can be used
It crushes again, but the shape of negative electrode active material can be destroyed.
In addition, cathode material of lithium ion battery may also include conductive additive (not shown), with sulfonated chitin one
It rises and is coated on negative electrode active material surface.It, can be by sulfonated chitin to negative since sulfonated chitin is in itself without electric conductivity
While the surface of pole active material is modified, conductive additive is added, so that appropriateness improves electric conductivity.Conductive additive pair
The weight composition ratio of sulfonated chitin is, for example, less than equal to 5, preferably less than or equal to 2.5.If the excessive conduction of addition adds
Add agent, sulfonated chitin will be influenced be fixed on the fixed effect on negative electrode active material surface.Conductive additive may include but not
Be limited to carbon black, acetylene black, carbon nanotubes, conductive carbon fibre, graphene, furnace black, Delanium, aquadag, copper powder, zinc powder,
Nickel powder, silver powder or its combination.
Hereinafter, the cathode material of lithium ion battery according to another embodiment of the present invention will be illustrated.
Fig. 2 is a kind of diagrammatic cross-section of cathode material of lithium ion battery according to another embodiment of the present invention.
With reference to Fig. 2, the cathode material of lithium ion battery 200 of the present embodiment may include negative electrode active material 202 and with sulphur
It is acidified the decorative layer 204 obtained by the surface of chitosan-modified negative electrode active material 202, in other words, the table of negative electrode active material 202
Face has the decorative layer 204 containing sulfonated chitin.In addition, the display of decorative layer 204 of Fig. 2 is coated on negative electrode active material 202
In whole surface, but actually decorative layer 204 may also only coating negative electrode active material 202 part surface.Negative electrode active
Substance 202 is for example selected from least one of group being made up of：Native graphite, Delanium, carbon alloy, surface metal
Carbon material, metatitanic acid salt, silicon, silica and silicon-carbon alloy are modified, but not limited to this.As for the weight average of sulfonated chitin
The parameters such as molecular weight, method of modifying and modification amount, can refer to an embodiment, so it will not be repeated.
In addition, the cathode material of lithium ion battery 200 of the present embodiment may also include conductive additive (not shown), so as to
Appropriateness improves electric conductivity.The weight composition ratio of conductive additive p-sulfonic acid chitin is, for example, less than equal to 5, is preferably less than
Equal to 2.5.And the species of conductive additive can also refer to an embodiment, so it will not be repeated.
Various experiments are exemplified below come the effect of verifying the present invention, but the invention is not limited in following contents.
Experimental example 1
First, sulfonated chitin water soluble liquid is prepared.First by 4 grams of sulfonated chitin, (weight average molecular weight Mw is
140,000) add in 36 grams of water, to form sulfonated chitin water soluble liquid of the concentration as 10% (weight percent).Then,
1.2 grams of carbon blacks as conductive additive are mixed in sulfonated chitin water soluble liquid, 30 points are stirred under about 25 DEG C of room temperature
Then clock adds in 34.8 grams of native graphite (being purchased from Rong Tan companies) and is used as negative electrode active material, in about 25 DEG C of room temperature
The cathode material of lithium ion battery of lower stirring 30 minutes, then dry water removal, i.e. completion experimental example 1.
Comparative example 1
The chitin water soluble liquid not modified is prepared, by 4 grams of the chitin (weight average molecular weight 2400) not modified
It adds in 36 grams of water, to form concentration as the 10% chitin water soluble liquid not modified.In the chitin water soluble liquid not modified
The carbon black of middle 1.2 grams of mixing is used as conductive additive, is stirred under about 25 DEG C of room temperature 30 minutes, is then added in 34.8 grams
Native graphite (be purchased from Rong Tan companies) used as negative electrode active material, stir 30 minutes under about 25 DEG C of room temperature, then
The cathode material of lithium ion battery of comparative example 1 is completed in dry water removal.
<Different modifying material is to the property improvement of negative electrode active material>
Fig. 3 A are the SEM figures of the negative material of comparative example 1.Fig. 3 B are the SEM figures that Fig. 3 A amplify 10 times.Fig. 4 A are experimental examples
The SEM figures of 1 negative material.Fig. 4 B are the SEM figures that Fig. 4 A amplify 10 times.
First, referring to Fig. 3 A, Fig. 3 B, Fig. 4 A and Fig. 4 B, the lithium ion battery before and after sulfonated chitosan-modified is used negative
Pole material has no significant difference on mode of appearance, and is still dispersity between negative electrode active material, has no caking phenomenon.
Secondly, by the cathode material of lithium ion battery obtained by experimental example 1 and comparative example 1, respectively with high-carbon acid propylene
Electrolyte (diethyl carbonate (diethyl carbonate, DEC) of 33% propene carbonate+67%) mixing of ester concentration
After lithium ion battery is made, three circle chemical conversions (formation), then the variation with the pole piece of both SEM observations are carried out with 0.1C.
Using the lithium ion battery made by the negative material of experimental example 1, it is electrolysed in the propene carbonate that concentration is 33%
Under liquid, after three circle of 0.1C chemical conversions, the native graphite through sulfonated chitosan-modified still maintains original pole piece appearance.However,
Use the lithium ion battery made by the cathode material of lithium ion battery of comparative example 1, after being melted into three circles under the same conditions, pole
Piece substantially expands and peeling phenomenon is substantially visual.It more particularly, can be referring to Fig. 5 A, Fig. 5 B, Fig. 6 A and Fig. 6 B.
Fig. 5 A be experimental example 1 negative material concentration be 33% propene carbonate electrolyte under, with 0.1C be melted into three
SEM figures after circle.Fig. 5 B are the SEM figures that Fig. 5 A amplify 4 times.Fig. 6 A are the negative materials of comparative example 1 in the carbon that concentration is 33%
Under acid propylene ester electrolyte, schemed with the SEM after three circle of 0.1C chemical conversions.Fig. 6 B are the SEM figures that Fig. 6 A amplify 4 times.
As fig. 5 a and fig. 5b, the native graphite after sulfonated chitosan-modified of experimental example 1 is 33% in concentration
Propene carbonate electrolyte under, with 0.1C chemical conversion three circle after, solid electrolyte (solid electrolyte
Interphase, SEI) film is less, and native graphite is substantially still possessed as former state.It reviews shown in Fig. 6 A and Fig. 6 B, uses comparative example 1
Negative material made by lithium ion battery, after being melted into three circles under the same conditions, a large amount of hyperplasia of SEI films, and graphite
The state that pops is presented in grain.
<Different modifying material influences the charge and discharge of lithium ion battery>
Fig. 7 is the lithium-ion electric being mixed by the negative material of experimental example 1 and the electrolyte of high carbon acid propylene ester concentration
The charge/discharge graph in pond.
As shown in Figure 7, the negative material of experimental example 1 can generate the effect of protection materials structure, inhibit propene carbonate
Behavior is embedded in altogether, and lithium ion battery is made to charge normal/discharge.
Fig. 8 is the lithium-ion electric being mixed by the negative material of comparative example 1 and the electrolyte of high carbon acid propylene ester concentration
The charge/discharge graph in pond.
As shown in Figure 8, since the voltage of charging curve is not dropped to close to 0V, represent that electrolyte is persistently carried out with native graphite
Chemical reaction, lithium ion battery can not charge normal, and discharge and abnormality is also presented (such as almost overlapping of the position on the left of Fig. 8
Shown in the 1st discharge curve together, the 2nd discharge curve and the 3rd discharge curve).Explained from another viewpoint, be because
Because the lasting common embedded behavior of high concentration propene carbonate when can not be blocked in 0.7V for the negative material of comparative example 1,
Material structure, which is persistently disintegrated, causes lithium ion battery that can not charge normal/discharge.
Fig. 9 is that electrolyte of experimental example 1 and comparative example 1 the negative material respectively with high carbon acid propylene ester concentration mixes system
Into lithium ion battery charge/discharge cycle graph.
Fig. 9 is refer to, the native graphite after sulfonated chitosan-modified of experimental example 1 can be with the carbon of tolerable concentration 33%
Acid propylene ester electrolyte, and the lithium ion battery made by it has splendid cycle life.Review, comparative example 1 not change
The chitin of matter then can not be charged normal/discharged come the lithium ion battery made by the native graphite modified.
<Different modifying amount is to the property improvement of negative electrode active material>
Comparative example 2,2~experimental example of experimental example 5
According to component listed by the following table 1, comparative example 2, experimental example are prepared using the preparation method identical with above-mentioned experimental example 1
The cathode material of lithium ion battery of 2~experimental example 5.
Table 1
Figure 10 be comparative example 2,2~experimental example of experimental example 5 negative material water contact angle change curve.
Referring to Figure 10, the hydrophily of the negative material of comparative example 2 (unmodified native graphite) is poor.In comparison, pass through
The native graphite of sulfonated chitosan-modified, more than modification amount 0.15% (experimental example 2), the hydrophily of negative material has aobvious
The improvement (3~experimental example of experimental example 5) of work.
<Influence of the conductive additive to lithium ion battery property>
Experimental example 6
Sulfonated chitin water soluble liquid is prepared, 0.2 gram of sulfonated chitin (Mw=140,000) is added in 42 grams of water
In solution, to form concentration as 10% sulfonated chitin water soluble liquid.Then add in 39.8 grams of native graphite and (be derived from flourish carbon
Company) it is used as negative electrode active material, it is stirred under about 25 DEG C of room temperature 30 minutes, then dry water removal, that is, complete experiment
The cathode material of lithium ion battery of example 6.
By the cathode material of lithium ion battery obtained by experimental example 6 and the electrolyte (33% of high carbon acid propylene ester concentration
Propene carbonate+67% diethyl carbonate (diethyl carbonate, DEC)) be mixed and made into lithium ion battery after, into
The circle chemical conversion of row three (formation).Chemical conversion condition is identical with chemical conversion condition used in above-mentioned experimental example 1 and comparative example 1, therefore not
It repeats again.
Figure 11 is the lithium-ion electric being mixed by the negative material of experimental example 6 and the electrolyte of high carbon acid propylene ester concentration
The charge/discharge graph in pond.Figure 12 is to mix system with the electrolyte of high carbon acid propylene ester concentration by the negative material of experimental example 6
Into lithium ion battery charge/discharge cycle graph.
As shown in figure 11, experimental example 6 without add in conductive additive negative material, obtained by lithium ion battery
Also it can charge normal/discharge.Referring also to Figure 11 and Figure 12 and referring again to Fig. 7 and Fig. 9, experimental example 1 using carbon black as leading
The negative material of electric additive, obtained by lithium ion battery have larger gram capacitance, represent by addition conduction add
Agent is added to help to improve the electric conductivity of negative material.Also, the cycling of lithium ion battery can be promoted by addition conductive additive
Service life and stability.
In conclusion the manufacturing method of cathode material of lithium ion battery according to the present invention can it is whole at normal temperatures into
Row, and manufacturing process does not take simply.In addition, the present invention by by sulfonated chitosan-modified negative electrode active material table
Face can inhibit the common embedded behavior of propene carbonate under high concentration propene carbonate electrolyte environment, have acquisition excellent
The electrolyte of resistance to propene carbonate effect cathode material of lithium ion battery.
Although the present invention is disclosed as above with embodiment, however, it is not to limit the invention, any technical field
Middle tool usually intellectual, it is without departing from the spirit and scope of the present invention, therefore of the invention when can make a little change and retouching
Protection domain subject to be defined depending on claim.
Claims (16)
1. a kind of manufacturing method of cathode material of lithium ion battery, which is characterized in that including：
Prepare monosulfonic acid chitin water soluble liquid；And
Negative electrode active material is surface modified using the sulfonated chitin water soluble liquid.
2. the manufacturing method of cathode material of lithium ion battery according to claim 1, which is characterized in that described in progress
Before surface modification, hybrid conductive additive in the sulfonated chitin water soluble liquid is additionally included in.
3. the manufacturing method of cathode material of lithium ion battery according to claim 2, which is characterized in that the conduction adds
Agent is added to be less than or equal to 5 to the weight composition ratio of the sulfonated chitin.
4. the manufacturing method of cathode material of lithium ion battery according to claim 3, which is characterized in that the conduction adds
Agent is added to be less than or equal to 2.5 to the weight composition ratio of the sulfonated chitin.
5. the manufacturing method of cathode material of lithium ion battery according to claim 1, which is characterized in that described sulfonated
The weight average molecular weight of chitin is between 2,000~1,000,000.
6. the manufacturing method of cathode material of lithium ion battery according to claim 1, which is characterized in that compared with described
The full dose of negative electrode active material, the modification amount of the sulfonated chitin is 0.05%~20%.
7. the manufacturing method of cathode material of lithium ion battery according to claim 6, which is characterized in that compared with described
The full dose of negative electrode active material, the modification amount of the sulfonated chitin is 0.15%~10%.
8. a kind of cathode material of lithium ion battery, which is characterized in that including：
Negative electrode active material, the surface of the negative electrode active material have the decorative layer containing sulfonated chitin.
9. cathode material of lithium ion battery according to claim 8, which is characterized in that the decorative layer further includes conduction and adds
Add agent.
10. cathode material of lithium ion battery according to claim 9, which is characterized in that the conductive additive is to institute
The weight composition ratio for stating sulfonated chitin is less than or equal to 5.
11. cathode material of lithium ion battery according to claim 10, which is characterized in that the conductive additive is to institute
The weight composition ratio for stating sulfonated chitin is less than or equal to 2.5.
12. cathode material of lithium ion battery according to claim 9, which is characterized in that the conductive additive is carbon
Black, carbon nanotubes, conductive carbon fibre, graphene, furnace black, Delanium, aquadag, copper powder, zinc powder, nickel powder, silver powder or its
Combination.
13. cathode material of lithium ion battery according to claim 8, which is characterized in that the sulfonated chitin
Weight average molecular weight is between 2,000~1,000,000.
14. cathode material of lithium ion battery according to claim 8, which is characterized in that compared with the negative electrode active
The full dose of substance, the modification amount of the sulfonated chitin is 0.05%~20%.
15. cathode material of lithium ion battery according to claim 14, which is characterized in that compared with the negative electrode active
The full dose of substance, the modification amount of the sulfonated chitin is 0.15%~10%.
16. cathode material of lithium ion battery according to claim 8, which is characterized in that the negative electrode active material choosing
From at least one of group being made up of：Native graphite, Delanium, carbon alloy, surface metal modification carbon material, titanium
Barbiturates, silicon, silica and silicon-carbon alloy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW105137588A TWI600204B (en) | 2016-11-17 | 2016-11-17 | Anode material for lithium ion battery and manufacturing method thereof |
| TW105137588 | 2016-11-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108075112A true CN108075112A (en) | 2018-05-25 |
Family
ID=60719632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710076350.XA Withdrawn CN108075112A (en) | 2016-11-17 | 2017-02-13 | Negative electrode material for lithium ion battery and method for producing same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108075112A (en) |
| TW (1) | TWI600204B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115240987A (en) * | 2022-05-17 | 2022-10-25 | 中国计量大学 | Woven mesh-shaped composite structure carbon and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5620587A (en) * | 1994-10-14 | 1997-04-15 | Nakamura; Tadamasa | Water processing method and apparatus |
| CN102760883A (en) * | 2012-07-13 | 2012-10-31 | 中国科学院广州能源研究所 | Novel chitosan used for lithium ion cell and derivative water-based binder of chitosan |
| KR20120128865A (en) * | 2011-05-18 | 2012-11-28 | 관동대학교산학협력단 | A single reactor microbial fuel cell using sediment |
-
2016
- 2016-11-17 TW TW105137588A patent/TWI600204B/en active
-
2017
- 2017-02-13 CN CN201710076350.XA patent/CN108075112A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5620587A (en) * | 1994-10-14 | 1997-04-15 | Nakamura; Tadamasa | Water processing method and apparatus |
| KR20120128865A (en) * | 2011-05-18 | 2012-11-28 | 관동대학교산학협력단 | A single reactor microbial fuel cell using sediment |
| CN102760883A (en) * | 2012-07-13 | 2012-10-31 | 中国科学院广州能源研究所 | Novel chitosan used for lithium ion cell and derivative water-based binder of chitosan |
Non-Patent Citations (2)
| Title |
|---|
| YEONG-TARNG SHIEH 等: "Graphene oxide-assisted dispersion of carbon nanotubes in sulfonated chitosan-modified electrode for selective detections of dopamine, uric acid, and ascorbic acid", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| 周享春 等: "碘在甲壳素修饰碳糊电极上的伏安行为研究", 《华中师范大学学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115240987A (en) * | 2022-05-17 | 2022-10-25 | 中国计量大学 | Woven mesh-shaped composite structure carbon and preparation method and application thereof |
| CN115240987B (en) * | 2022-05-17 | 2023-10-20 | 中国计量大学 | Woven mesh composite structure carbon and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201820690A (en) | 2018-06-01 |
| TWI600204B (en) | 2017-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lancry et al. | Leaching chemistry and the performance of the Mo6S8 cathodes in rechargeable Mg batteries | |
| Zhao et al. | Crosslinked chitosan networks as binders for silicon/graphite composite electrodes in li-ion batteries | |
| CN103208615B (en) | Silicon-carbon composite material, and preparation method and application thereof | |
| CN106340649A (en) | Preparation method of lithium ferric phosphate cathode slurry | |
| CN105810915A (en) | Preparation of graphene-coated sulfur-embedded ordered mesoporous carbon sphere composite material and application of ordered mesoporous carbon sphere composite material as lithium-sulfur battery positive electrode material | |
| Uono et al. | Optimized structure of silicon/carbon/graphite composites as an anode material for Li-ion batteries | |
| CN106784815A (en) | A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery | |
| CN106992297A (en) | A kind of preparation method and application of ternary battery composite anode material | |
| CN106159236A (en) | A kind of quick charge lithium titanate composite negative pole pole piece and lithium ion battery | |
| CN101593825B (en) | Negative pole made of nanometer antimony/graphite nanosheet composite material of lithium ion battery and preparation method thereof | |
| CN103915623B (en) | The preparation method of nano porous metal sulfide rechargeable magnesium cell anode material | |
| CN106025268A (en) | Water-based lithium battery cathode slurry and preparation method thereof | |
| CN105591084A (en) | Negative electrode active material and preparation method thereof | |
| Karuppiah et al. | Water‐soluble green binder for Li4Ti5O12 anodes: Effect of binder choice on lithium storage | |
| CN104600292A (en) | Preparation method for carbon-graphene doubly modified lithium iron phosphate anode material | |
| CN107195885A (en) | A kind of carbon nanotube polymer lithium ion battery and preparation method thereof | |
| CN101593826A (en) | Lithium ion battery SnSb alloy/graphite nanosheet composite material negative pole and preparation method thereof | |
| Ramdhiny et al. | Design of multifunctional polymeric binders in silicon anodes for lithium‐ion batteries | |
| CN108075112A (en) | Negative electrode material for lithium ion battery and method for producing same | |
| CN110459738A (en) | Lithium ion battery anode glue size and preparation method thereof, positive plate, lithium ion battery | |
| CN105514433A (en) | Preparation method of graphene lithium ion battery anode material doped with copper zinc tin sulfide | |
| CN110277545A (en) | A kind of antimony/preparation method with ductility carbon compound cathode materials | |
| CN110571420B (en) | Method for synthesizing silicon/graphite/amorphous carbon/conductive carbon black quaternary composite material by using industrial metallurgical silicon | |
| CN105390679B (en) | A kind of capacitor type anode composite material of lithium ion battery and preparation method thereof | |
| Han et al. | Temperature‐Dependent Nanopolyhedron Carbon‐Decorated Sb for High‐Performance Lithium‐Ion Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180525 |