CN110112364A - A kind of MULTILAYER COMPOSITE negative electrode material and preparation method thereof and negative electrode tab, lithium battery - Google Patents
A kind of MULTILAYER COMPOSITE negative electrode material and preparation method thereof and negative electrode tab, lithium battery Download PDFInfo
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- CN110112364A CN110112364A CN201910345513.9A CN201910345513A CN110112364A CN 110112364 A CN110112364 A CN 110112364A CN 201910345513 A CN201910345513 A CN 201910345513A CN 110112364 A CN110112364 A CN 110112364A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 57
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010703 silicon Substances 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000002210 silicon-based material Substances 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000000748 compression moulding Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 230000036647 reaction Effects 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- 229910021384 soft carbon Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 230000005518 electrochemistry Effects 0.000 claims 1
- 229910021385 hard carbon Inorganic materials 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 235000012239 silicon dioxide Nutrition 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 239000002153 silicon-carbon composite material Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
A kind of MULTILAYER COMPOSITE negative electrode material and preparation method thereof and negative electrode tab, lithium battery, the preparation step of the MULTILAYER COMPOSITE negative electrode material is as follows: preparing multilayer presoma using silicon, silica, carbon as raw material, the first precursor layer mixture is obtained after silicon materials are mixed with binder, the second precursor layer mixture is obtained after silica, carbon material and binder are mixed, third precursor layer mixture is obtained after carbon material is mixed with binder；By the first, second, third precursor layer mixture according to sintering processes are carried out after the sequence compression molding of silicon layer, silicon/carbon dioxide mixed layer, carbon-coating, multilayer presoma is obtained；It is elemental silicon by the reducing silica in multilayer presoma, obtains MULTILAYER COMPOSITE negative electrode material.The present invention can generate finer and close solid electrolyte interface film, while the Volumetric expansion for inhibiting silicon materials to occur in charge and discharge process during first charge-discharge, to improve the first charge discharge efficiency of battery, cathode specific capacity and cycle performance of battery.
Description
Technical field
The invention belongs to field of power lithium ion battery technology more particularly to a kind of composite negative poles of power lithium-ion battery
Material.
Background technique
With popularizing for New-energy electric vehicle application, people require the cruising ability of power electric motor car higher and higher.
On power battery using the positive and negative electrode material of height ratio capacity to improve battery cruising ability play the role of it is particularly important.
Currently, cathode material of lithium-ion power battery is mainly graphite type material, the theoretical specific capacity of graphite is 372mAh/g, at this stage
The specific capacity of the graphite negative electrodes material of volume production has reached 360mAh/g or more, basically reaches the upper limit of graphite material, difficult
To meet the needs of people are to high energy density cells at this stage.
In recent years, the various novel anode materials with height ratio capacity are continuously developed out.Wherein, silicon materials are due to tool
Have a height ratio capacity, resourceful, and it is close with carbon material current potential the advantages that, become novel cathode material for lithium ion battery
Research hotspot.But silicon materials under de-/embedding lithium of high level there is serious bulk effect (volume expansion is greater than 400%),
It will lead to silicon particle rupture dusting, cause negative electrode material structure collapses, be detached from conductive grid, internal resistance is sharply increased, finally led
Cause the special capacity fade of negative electrode material rapid, the cycle performance of battery is deteriorated.
In order to improve volume expansion problem existing for silicon materials and improve the electric conductivity of electrode material, Publication No.
The Chinese invention patent application of CN108110233A discloses a kind of carbon-silicon composite material, which uses titanium dioxide
Silicon and carbon obtain presoma after two kinds of materials are mixed and are sintered, then by the silica in presoma as original material
It is reduced to elemental silicon, carbon-silicon composite material is made.After elemental silicon and carbon material are combined with each other by the composite material, it can slow down
The volume expansion problem of electrode material improves the first charge-discharge efficiency and energy density, increase of battery to a certain extent
The specific capacity of battery, but there are still improved space.
Summary of the invention
The purpose of the present invention is to provide a kind of with height ratio capacity, Gao Shouxiao and long circulation life by silicon, titanium dioxide
Silicon, negative electrode material of multilayered structure of carbon composition and preparation method thereof, and use the negative electrode tab and lithium battery of the negative electrode material.
To achieve the goals above, the present invention takes following technical solution:
A kind of preparation method of MULTILAYER COMPOSITE negative electrode material, comprising the following steps:
Multilayer presoma is prepared using silicon materials, silica, carbon material as raw material, after silicon materials are mixed with binder
To the first precursor layer mixture, the second precursor layer mixture is obtained after silica, carbon material and binder are mixed, it will
Carbon material obtains third precursor layer mixture after mixing with binder；
By the first precursor layer mixture, the second precursor layer mixture, third precursor layer mixture according to silicon
The sequence compression molding of layer, silicon/carbon dioxide mixed layer, carbon-coating；
The mixture of compression molding is sintered, multilayer presoma is obtained；
It is elemental silicon by the reducing silica in multilayer presoma, obtains MULTILAYER COMPOSITE negative electrode material.
Further, the mass percent of the silicon materials is 2%~35%, and the mass percent of earth silicon material is
3%~75%, the mass percent of carbon material is 20%~94%.
Further, the silicon materials be nano wire silicon and/or the carbon material be artificial graphite, it is natural graphite, hard
The mixture of one or more of carbon, soft carbon, carbonaceous mesophase spherules.
Further, the first precursor layer mixture, the second precursor layer mixture, third precursor layer are mixed
Object is molded into sheet under the pressure of 5MPa~36MPa respectively, folded according to the sequence of silicon layer, silicon/carbon dioxide mixed layer, carbon-coating
It bleeds off pressure and multilayer mixture is made.
Further, the step of sintering processes are as follows: by mixture under inert atmosphere or vacuum condition, in 600 DEG C~
1400 DEG C of temperature is sintered 1~36 hour.
Further, use electrochemical reducing by the reducing silica in the multilayer presoma for elemental silicon.
Further, the step of using electrochemical reducing to restore silicon is as follows: using the multilayer presoma as cathode, with
For graphite rod as anode, fuse salt carries out cell reaction as electrolyte under the protection of inert gas, will after the completion of electrolysis
Catholyte product cleaning, drying obtain MULTILAYER COMPOSITE negative electrode material.
Further, when cell reaction, electrolysis temperature is 500 DEG C~1400 DEG C, decomposition voltage is 1.2V~3.2V, electrolysis
Time 4~96 hours.
Further, after the completion of electrolysis, catholyte product is successively subjected to deionized water washing, pickling, deionized water
Washing, is finally dried.
Further, used when pickling concentration for 5~40% hydrochloric acid.
The present invention also provides a kind of MULTILAYER COMPOSITE negative electrode material, which uses preceding method system
At.
The present invention also provides a kind of negative electrode tab, the negative electrode tab includes signature MULTILAYER COMPOSITE negative electrode material.
The present invention also provides a kind of lithium battery, including positive plate and negative electrode tab, the negative electrode tab is signature negative electrode tab.
From the above technical scheme, the composition of cathode material of lithium-ion power battery is optimized in the present invention, adopts
Multi-layer compound structure is formed after being respectively formed different precursor layers with silicon, silica and carbon, carbon, by reducing silica
On the basis of elemental silicon, after keeping (nano wire) silicon and silica and carbon compound, (nano wire) silicon is in silica and (receives
Rice) it grows on carbon, so that finer and close solid electrolyte interface film (SEI film) can be generated during first charge-discharge,
To improve the first charge discharge efficiency and cathode specific capacity of battery, silicon and carbon compound while it can also play and inhibit silicon materials in charge and discharge
The effect that Volumetric expansion occurs in the process, to improve cycle performance of battery.The present invention can also reduce silicon-carbon cathode material
Preparation cost improves the problem of environmental pollution faced in traditional silicon based anode material production process.
Detailed description of the invention
Fig. 1 is the flow chart of the embodiment of the present invention；
Fig. 2 is a kind of schematic diagram that Si reduction is carried out using electrochemical reducing provided in an embodiment of the present invention.
A specific embodiment of the invention is described in more detail below in conjunction with attached drawing
Specific embodiment
In order to above and other objects of the present invention, feature and advantage can be become apparent from, the embodiment of the present invention is cited below particularly,
It is described below in detail.
Silicon/silicon dioxide of the invention/carbon MULTILAYER COMPOSITE negative electrode material is by three kinds of silicon, silica, carbon Material claddings
Manufactured multilayer materials, the multilayered structure include silicon layer, silicon/carbon dioxide mixed layer and carbon-coating, wherein the matter of silicon materials
Measuring percentage is 2%~35%, and the mass percent of earth silicon material is 3%~75%, and the mass percent of carbon material is
20%~94%.
As shown in Figure 1, the step of silicon/silicon dioxide of the invention/carbon multilayer materials preparation method, is as follows:
Multilayer precursor preparation step；Respectively using silicon, silica and carbon, carbon as initial feed, the first presoma is prepared
Layer, the second precursor layer and third precursor layer, wherein the first precursor layer is the silicon layer made of pure silicon compacting, preferably
Using nano wire silicon, the second precursor layer is the carbon-coating made of carbon material compacting, it is preferred to use nano-carbon material, before third
Driving body layer is silicon/carbon dioxide mixed layer made of suppressing after being mixed as silica and carbon material for initial feed, is preferably adopted
With nano-multicrystal silica and nano-carbon material；The dosage of layers of material is matched according to target product, and is separately added into appropriate
Binder carry out ball milling (ball milling 2~36 hours), the initial powder of each layer presoma is obtained, then 5MPa~36MPa's
Under the conditions of be compressed into tablet form object respectively, and according to silicon layer --- silicon/carbon dioxide layer --- carbon-coating sequence it is stacked after be pressed into
The mixing tablet of sandwich structure, the mixing tablet that compacting is obtained is under inert atmosphere or vacuum condition, in 600 DEG C
~1400 DEG C are sintered 1~36 hour, obtain the multilayer presoma with some strength；The additive amount of binder is according to the powder of each layer
The quality of body raw material and the compactness of presoma determine, additional amount is empirical value, the 2 of generally each layer powder material quality
~50%；Silica and carbon material are not needed according to specific proportions in silicon/carbon dioxide mixed layer, and the two can be with
It is mixed and made into silicon/carbon dioxide mixed layer in any proportion, then further according to the use of the other materials at two layers of the consumption proportion of the two
Amount；
Si reduction step；It is silicon that electrochemical reducing, which can be used, by the reducing silica in presoma, i.e., will be before multilayer
Body is driven as cathode, graphite rod and, as electrolyte, cell reaction is carried out under the protection of inert gas as anode, fuse salt,
Specific step is as follows: as shown in Fig. 2, using multilayer precursor as cathode, such as by multilayer presoma nickel foam according to Sanming City
Cathod system is made in connection Fe-Cr-Al wire after controlling formula package, and using high purity graphite stick as anode, cathode and anode are put into earthenware
In crucible, using crucible as electrolytic cell, heating equipment is crucible electrical resistance furnace, and power supply is D.C. regulated power supply, in inert gas shielding
Under electrolytic furnace in, with electrolysis temperature be 500 DEG C~1400 DEG C, decomposition voltage 1.2V~3.2V carries out cell reaction, when electrolysis
Between 4~96 hours；
Cleaning, drying steps；After the completion of electrolysis, it is cooled to room temperature to temperature and (is electrolysed and cooling overall process uses inertia
Gas is protected), catholyte product is taken out, deionized water washing --- pickling --- deionized water water is successively carried out
It washes, 80~200 DEG C of dry drying, obtain silicon/silicon dioxide/carbon multilayer materials in air.
Silica used in the present invention can be to analyze pure grade material, and carbon material can be artificial graphite, natural graphite, hard
The mixture of one or more of the materials such as carbon, soft carbon, carbonaceous mesophase spherules.Used inert gas can be argon gas.Electricity
Crucible used in solution reaction can be corundum crucible or stainless steel crucible, and fuse salt used in cell reaction can be chlorination
The fused salt mixt of one or more of calcium, magnesium chloride, potassium chloride, sodium chloride.The salt that concentration is 5~40% can be used when pickling
Acid.
It is core of the invention thought above, following will be combined with the drawings in the embodiments of the present invention, to the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are only a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of the every other embodiment that obtains, shall fall within the protection scope of the present invention.
Below by specific embodiment and comparative example, the present invention is further illustrated.It is arrived used in following the description
Reagent, material and instrument such as not special explanation, are conventional reagent, conventional material and conventional instrument, commercially available
It obtains, related reagent can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
The artificial graphite of the silica of 0.209g and 1.800g are mixed, the polyvinyl butyral that 0.05g is added is (viscous
Tie agent), then ball milling, the uniform powder of acquisition is as silicon/silicon dioxide layer precursor powder, by SiO2/ C mixed-powder
Be compressed into tablet form object, and the pure carbon powder of the pure silicon of 0.200g and 0.900g be also compressed into tablet form object respectively respectively, then according to
Si|SiO2/ C | C sequence is molded into the tablet of multilayered structure, and then mixing tablet is put into sintering furnace, is filled with argon gas,
It is warming up to 680 DEG C of sintering 13h preparation multilayer presomas；
Electronic conductive material connection is used to draw as cathode multilayer presoma, using high purity graphite stick as anode,
Using corundum crucible as electrolytic cell in electrolytic furnace, weighs 380 grams of calcium chloride (fuse salt) and be put into ceramic crucible, to crucible electrical resistance furnace
In be passed through argon gas, 1000 DEG C of heating melts fuse salt, cathode, anode is put into ceramic crucible, D.C. regulated power supply connection
Positive and negative anodes energization 2.8V is carried out cell reaction 46 hours；
After electrolysis, by catholyte product successively with deionized water washing, ultrasonic wave added 36% (mass fraction) salt
Pickling, deionized water washing, 120 DEG C of dry drying, obtain silicon/silicon dioxide/carbon MULTILAYER COMPOSITE negative electrode material in air.
Embodiment 2
The graphite of making of the silica of 0.618g and 2.600g people are mixed, the polyvinyl butyral of 0.18g is added, so
Ball milling afterwards, the uniform powder of acquisition is as silicon/silicon dioxide layer precursor powder, by SiO2/ C mixed-powder is tabletted
Shape object, and the pure carbon powder of 0.800g pure silicon and 0.200g is also compressed into tablet form object respectively respectively, then according to SiO2|SiO2/C|
C sequence is molded into the tablet of three-decker, and then mixing tablet is put into sintering furnace, argon gas is filled with, is warming up to 850 DEG C
It is sintered 8h and prepares multilayer presoma；
Electronic conductive material connection is used to draw as cathode multilayer presoma, using high purity graphite stick as anode,
It using stainless steel crucible as electrolytic cell in electrolytic furnace, weighs 400 grams of calcium chloride and is put into stainless steel crucible, lead into crucible electrical resistance furnace
Enter argon gas, 1000 DEG C of heating makes its fusing, cathode, anode are put into stainless steel crucible, and D.C. regulated power supply connects positive and negative anodes
Energization 3.0V is carried out cell reaction 32 hours；
After electrolysis, by catholyte product successively with deionized water washing, 36% chlorohydric acid pickling of ultrasonic wave added, go from
Sub- water washing, 120 DEG C of dry drying, obtain silicon/silicon dioxide/carbon MULTILAYER COMPOSITE negative electrode material in air.
Embodiment 3
The artificial graphite of the silica of 0.991g and 2.800g are mixed, the polyvinyl butyral of 0.22g is added, so
Ball milling afterwards obtains uniform powder as silicon/silicon dioxide layer precursor powder, SiO2/C mixed powder is compressed into tablet form
Object, and the pure carbon powder of the pure silicon of 0.100g and 0.400g is also compressed into tablet form object respectively respectively, then according to SiO2|SiO2/C|
C sequence is molded into the tablet of three-decker, then puts into a sintering furnace, is filled with argon gas, and it is more to be warming up to 920 DEG C of sintering 7h preparations
Layer presoma；
Electronic conductive material connection is used to draw as cathode multilayer presoma, using high purity graphite stick as anode,
Using corundum crucible as electrolytic cell in electrolytic furnace, weighs 400 grams of sodium chloride and be put into ceramic crucible, argon is passed through into crucible electrical resistance furnace
Gas, 1300 DEG C of heating make its fusing, cathode, anode are put into ceramic crucible, and D.C. regulated power supply connects positive and negative anodes and is powered
3.1V is carried out cell reaction 40 hours；
After electrolysis, by catholyte product successively with deionized water washing, 32% chlorohydric acid pickling of ultrasonic wave added, go from
Sub- water washing, 150 DEG C of dry drying, obtain silicon/silicon dioxide/carbon MULTILAYER COMPOSITE negative electrode material in air.
Comparative example
Comparative example prepares carbon silicon composite cathode material using method provided by CN108110233A Chinese invention patent application
Material, specific solution are as follows:
It is equal to weigh 0.6 gram of silica, 2.52 grams of soft carbon powder and the mixing of 0.08 gram of polyvinyl butyral
Even, forming mixture, (in mixture, the mass fraction of silica is 18.75%, the mass fraction of soft carbon powder is
78.75%, the mass fraction of polyvinyl butyral is 2.5%), mixture to be pressed and molded to compacting under the pressure of 10MPa
Slabbing object, tablet is put into sintering furnace, is filled with argon gas, is warming up to 600 DEG C, after being sintered 12h, obtains presoma；
It uses electronic conductive material connection to draw as cathode using high purity graphite stick as anode presoma be electrolysed
Using ceramic crucible as electrolytic cell in furnace, 60 grams of potassium chloride, 150 grams of magnesium chloride, 90 grams of sodium chloride (potassium chloride: magnesium chloride: chlorine are weighed
Change sodium=0.2:0.5:0.3) it is put into ceramic crucible, argon gas is passed through into crucible electrical resistance furnace, 700 DEG C of heating keeps fuse salt molten
Change, anode and cathode is put into ceramic crucible, D.C. regulated power supply connects positive and negative anodes energization 2.8V, carries out cell reaction 60 hours；
After cell reaction, by catholyte product successively with deionized water washing, 36% chlorohydric acid pickling of ultrasonic wave added,
Deionized water washing, finally, 150 DEG C of dryings in air, obtain Si-C composite material.
Using composite material made from embodiment 1-3 and comparative example as negative electrode material, work is prepared using conventional negative electrode tab
Negative electrode tab is made in skill, i.e., is coated on copper foil composite material, conductive agent, binder after mixing, obtains negative electrode tab, and normal
The ternary material positive plate collocation of rule is assembled into the full battery of model 2025.
Battery specific capacity will be carried out using battery made from the negative electrode material of embodiment 1-3 and comparative example and cycle performance is surveyed
Examination, the result of test are as shown in the table:
From table 1 it follows that silicon/silicon dioxide/carbon multilayer the multicomponent composite materials prepared using the method for the present invention
There is higher specific capacity and first charge-discharge efficiency and longer cycle life compared to monolayer silicon/carbon composite.This hair
The bright negative electrode material that multilayered structure is made of different materials, dilation of the material layer of different component in cyclic process is not
Together, layers of material can not only play the volume expansion for inhibiting cathode to generate in cyclic process, improve the cycle performance of battery,
And silicon layer and carbon-coating are being prepared respectively in silicon/carbon-coating two sides, the negative electrode material of high capacity can be obtained, to improve battery
Energy density.Composite negative pole material of the invention is by repeatedly suppressing and controlling reaction time and reaction temperature and voltage
Etc. conditions, the negative electrode material of different proportion component required for can precisely obtaining, thus improve the first charge discharge efficiency of negative electrode material with
And electrical property.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to embodiment illustrated herein, and is to fit to consistent with the principles and novel features disclosed in this article
Widest range.
Claims (13)
1. a kind of preparation method of MULTILAYER COMPOSITE negative electrode material, which comprises the following steps:
Multilayer presoma is prepared using silicon materials, silica, carbon material as raw material, the is obtained after silicon materials are mixed with binder
One precursor layer mixture obtains the second precursor layer mixture after mixing silica, carbon material and binder, by carbon materials
Material obtains third precursor layer mixture after mixing with binder；
By the first precursor layer mixture, the second precursor layer mixture, third precursor layer mixture according to silicon layer, two
The sequence compression molding of silica/carbon mixed layer, carbon-coating；
The mixture of compression molding is sintered, multilayer presoma is obtained；
It is elemental silicon by the reducing silica in multilayer presoma, obtains MULTILAYER COMPOSITE negative electrode material.
2. the preparation method of MULTILAYER COMPOSITE negative electrode material as described in claim 1, it is characterised in that: the quality of the silicon materials
Percentage is 2%~35%, and the mass percent of earth silicon material is 3%~75%, and the mass percent of carbon material is
20%~94%.
3. the preparation method of MULTILAYER COMPOSITE negative electrode material as claimed in claim 1 or 2, it is characterised in that: the silicon materials are
Nano wire silicon and/or the carbon material be one of artificial graphite, natural graphite, hard carbon, soft carbon, carbonaceous mesophase spherules or
Several mixtures.
4. the preparation method of MULTILAYER COMPOSITE negative electrode material as claimed in claim 1 or 2, it is characterised in that: before described first
Body layer mixture, the second precursor layer mixture, third precursor layer mixture are driven respectively in the pressure lower die of 5MPa~36MPa
It is pressed into sheet, stacks according to the sequence of silicon layer, silicon/carbon dioxide mixed layer, carbon-coating and is pressed into multilayer mixture.
5. the preparation method of MULTILAYER COMPOSITE negative electrode material as claimed in claim 1 or 2, it is characterised in that: the step of sintering processes
Suddenly are as follows: by mixture under inert atmosphere or vacuum condition, be sintered 1~36 hour in 600 DEG C~1400 DEG C of temperature.
6. the preparation method of MULTILAYER COMPOSITE negative electrode material as claimed in claim 1 or 2, it is characterised in that: also using electrochemistry
Reducing silica in the multilayer presoma is elemental silicon by former method.
7. the preparation method of MULTILAYER COMPOSITE negative electrode material as claimed in claim 6, it is characterised in that: use electrochemical reducing
The step of restoring silicon is as follows:
Using the multilayer presoma as cathode, using graphite rod as anode, fuse salt is as electrolyte, in the guarantor of inert gas
Shield is lower to carry out cell reaction, after the completion of electrolysis, by catholyte product cleaning, drying, obtains MULTILAYER COMPOSITE negative electrode material.
8. the preparation method of MULTILAYER COMPOSITE negative electrode material as claimed in claim 7, it is characterised in that: when cell reaction, electrolysis
Temperature is 500 DEG C~1400 DEG C, decomposition voltage is 1.2V~3.2V, electrolysis time 4~96 hours.
9. the preparation method of MULTILAYER COMPOSITE negative electrode material as claimed in claim 7 or 8, it is characterised in that:, will after the completion of electrolysis
Catholyte product successively carries out deionized water washing, pickling, deionized water washing, finally dries.
10. the preparation method of MULTILAYER COMPOSITE negative electrode material as claimed in claim 9, it is characterised in that: use concentration when pickling
For 5~40% hydrochloric acid.
11. a kind of MULTILAYER COMPOSITE negative electrode material, it is characterised in that: use the described in any item MULTILAYER COMPOSITEs of claims 1 to 10
The preparation method of negative electrode material is made.
12. a kind of negative electrode tab, it is characterised in that: the negative electrode tab includes MULTILAYER COMPOSITE negative electrode material described in claim 11.
13. a kind of lithium battery, including positive plate and negative electrode tab, it is characterised in that: the negative electrode tab is described in claim 12
Negative electrode tab.
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