CN108390018A - The preparation method and its usage of three-dimensional honeycomb shape nanosizing Si - Google Patents
The preparation method and its usage of three-dimensional honeycomb shape nanosizing Si Download PDFInfo
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- CN108390018A CN108390018A CN201810176501.3A CN201810176501A CN108390018A CN 108390018 A CN108390018 A CN 108390018A CN 201810176501 A CN201810176501 A CN 201810176501A CN 108390018 A CN108390018 A CN 108390018A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the preparing technical fields of nano Si,It is related to the preparation method and its usage of three-dimensional honeycomb shape nanosizing Si,It is to be added in electrolyte metal solion before 0.2~5 μm of particle carbon coating by d50,It carries out ultrasonic wave or mulser is evenly dispersed,Make the attached sorption metal ion of micron order Si particle surfaces,After micron order Si particle surfaces being coated by carbon material,When being etched to the inside Si using the mixed solution of HF solution or HF and HO,Utilize metal ion attachment point,Quickly punching is initiated to the inside Si,To reach cutting micron Si internal structures,Form the perfect nanosizing space structure of three-dimensional space network honeycomb structure,It is advantageous to volume expansion of the lithium ion of lithium ion battery inside Si during deintercalation,It avoids the prior art and causes internal dusting because of volume expansion,Destroy electrode structure,The deficiency of cycle life of lithium ion battery rapid decay,The present invention is used for lithium ion battery negative material,Generated cycle performance is extremely excellent,Almost decaying is seldom.
Description
Technical field
The invention belongs to the preparing technical field of nano Si, refer in particular to a kind of three-dimensional honeycomb shape nanosizing Si preparation method and
Its purposes.
Background technology
It is that the electrochemical energy storage mainly showed has extended cycle life mainly because its is environmental-friendly with lithium ion battery, self discharge
Small, the energy density feature high with respect to other class batteries receives great favor, but with the development of new-energy automobile, state
Ministry of Industry and Information of family, the propositions such as Department of Science and Technology to the year two thousand twenty strive for that realization battery cell capacity density reaches 350wh/kg, and system will reach
The target of 260wh/kg, manufacturing cost will be reduced to 1 yuan every watt hereinafter, reaching this target, and country is every year to new energy vehicle
Subsidy can fully phase out, and by the raising of enterprise self-determining technology, participate in market competition, and select the superior and eliminate the inferior, but graphite traditional at present
Negative material or hard, soft carbon negative material cannot be satisfied the requirement of this target at all, and urgent need develops low cost, high power capacity
Next-generation battery material, current nickelic ternary+silicon-carbon composite cathode will become power battery mainstay material system, Si materials reason
By capacity about 4200mAh/g, as many as nearly 10 times are higher by than conventional graphite class cathode, soft or hard carbon negative pole material, is managed than silicon monoxide
2.5 times are higher by by capacity, but Si (silicon) volume expansions during height removal lithium embedded are up to 300% or more, can cause
The problem of dusting, peeling, destroys battery electric machine structure, also results in the generation that Si particle surfaces constantly form SEI films, causes
Electrolyte constantly persistently consumes, and seriously affects the cycle performance of battery, in order to solve Si materials in lithium ion battery applications process
In, it reduces volume expansion and causes bad problem, by Si nanosizings, village hollowing, Si- graphite is compound and synthesis SiO materials are numerous and confused
It comes out, in terms of existing market pattern, SiO is also high-capacity cathode material research direction, relatively a small amount of mixed in actual production
Application is closed, but SiO theoretical capacities also have 1700mAh/g or so, but SiO still suffers from a big problem at present, imitates for the first time
Rate is too low, can about reach highest 60%, this is primarily due to decision, basic nothing caused by the unique crystal structure of SiO materials
Method significantly, is individually used for battery cathode.
100nm or less simple substance nano silicon material is because its manufacturing cost is relatively high, and flood tide industrialized production is also by certain
Equipment limit, the problem of lithium ion battery applies in negative material, is not easy to disperse, easily reunite, after reunion just
Function of the nano-silicon because of low thermal expansion can be lost, so whole world scientific research personnel also pays close attention to micro- rule structure of silicon at present
Research and development application, i.e., will reach the performance of the low bulk after the nanosizing of Si, be not easy to reunite after silicon nanosizing again, while again
Want can the supply of flood tide industrialized production, realization reduces cost this requirement, and method of the invention is exactly toward this some aspects research
Development and production, can flood tide production, and height ratio capacity of the silicon-based anode in lithium ion battery can be increased substantially, had simultaneously
The lithium ion battery negative material of optimal cycle efficieny long-life, after 300 weeks recycle, the dough softening keeps capacity to exist less than 15%
85%, it is maintained at 90% than 300 cycle efficienies of current graphite cathode and approaches, be the universal ideal material of next-generation lithium ion battery
One of material.
Invention content
The object of the present invention is to provide a kind of preparation method and its usages of three-dimensional honeycomb shape nanosizing Si.
The object of the present invention is achieved like this：
The method that micron order Si prepares three-dimensional honeycomb shape nanosizing Si, includes the following steps：
(1) it is 0.2~5 μ by D50 (the cumulative particle sizes percentile of sample grain size corresponding when reaching 50%)
The simple substance Si particle powders of m, are added in electrolytic etching of metal matter solution, and the electrolytic etching of metal matter solution concentration being added after simple substance Si is
0.005~5mol/L, solid-to-liquid ratio are 3~38%：97~62%, it is evenly dispersed using ultrasonic wave or the vibration of mulser or magnetic wave,
Jitter time be 10~300min, make the attached sorption metal ion of simple substance Si particle surfaces, using centrifuge or compression filtering or
Vacuum filtration or spray drying or evaporation drying obtain relatively dry, the attached suction in surface has the micron order Si granular materials of metal ion
Material；
(2) the Si granular materials for obtaining step (1) carries out carbon coating, obtains carbon-coated Si granular materials；
(3) the carbon-coated Si granular materials that step (2) obtains is added in deionized water solution or ethanol solution, is controlled
Solid-to-liquid ratio processed is 3~40%：97~60%, evenly dispersed to carry out, jitter time is 10~300min；
(4) dispersion that step (3) obtains is added in the mixed solution of HF solution or HF and HO- and is mixed, wherein
A concentration of 3~30%, HO- of HF a concentration of 0.1~10%, incorporation time is 5~500min, is realized to quarter of Si granular materials
Erosion punching；
(5) the Si granular materials by step (4) etching punching is dried or is sprayed by natural subsidence or centrifugation or evaporation
Mist drying separation solid-liquid, obtains relatively dry, Si particle surfaces by the Si particle powder materials of carbon-coated cellular nano.
Above-mentioned carbon coating is to make carbon coating in Si particle surfaces through high temperature carbonization by more than one the substance that carbonizes
Carbon coating layer is formed, carbonization temperature is 380~1380 DEG C, and carbonization time is 1~12 hour；Or the carbon coating is by one kind
It is above can charring gas generated by Pintsch process and be deposited on the carbides of Si particle surfaces and form carbon coating layer, the carbon
The volume ratio of clad and micron order Si particles is 3~95%：97~5%.
The above-mentioned substance that carbonizes is：High molecular polymer phenolic resin, polypropylene be fine, epoxide resin, graphene oxide,
Pitch, sucrose, starch, glucose；It is described can charring gas be：Methane, acetylene, ethylene, ethane, the third ethylene, propane.
Above-mentioned carbonization temperature is 750~1150 DEG C, and carbonization time is 1.5~6 hours.
Above-mentioned simple substance Si be 98~99.9999% with purity coarse material, by dry ball milling or wet ball grinding or
The simple substance Si particle powder materials that the D50 of the mechanical ball mill method processing of efficient multidimensional ball milling or the ball milling that resonates is 0.2~5 μm
Material, or utilize the simple substance Si particle powder materials that semiconducter IC circular wafer or the D50 of photovoltaic cell processing are 0.2~5 μm
Material.
Above-mentioned electrolytic etching of metal matter solution is metal NO3- solion or metal SO4 2-Solion or metal OH-ion
Solution.
The three-dimensional honeycomb shape nanosizing Si prepared with the micron order Si methods for preparing three-dimensional honeycomb shape nanosizing Si
Purposes, can be individually used for extra-high capacity than lithium ion battery negative material, or by natural graphite, artificial graphite, interphase
Microballoon graphitization, hard carbon, soft carbon negative material more than one material mixed with the three-dimensional honeycomb shape nanosizing Si
It is even be applied to lithium ion battery in, produce high power capacity than negative material.
The present invention using the micron order Si particle powder materials that are routinely easy to get, by the attached sorption metal of its surface relative spacing from
Son is mixed using the solution of HF solution or HF and HO-, and using metal ion (caing be compared to nanometer drill bit) attachment point, it is quickly right to be formed
Punch-cuts are penetrated inside Si, are punched in etching, and carbon coating the surfaces Si, is generated in etching process, inside carbon-coating huge
Internal stress (can be compared to power source), be to realize perfection by the quick punch-cuts of metal ion inside the Si particles after carbon coating
Three dimensions nanosizing honeycomb structure, not only had the nanosizing function of Si but be provided simultaneously with Si microns of level characteristics and easily point
The advantages of dissipating, being not easy to reunite is not easy to expand and cause dusting and reunion, be formed in the frequent charge and discharge process of lithium ion height
Cycle performance is excellent, and coulombic efficiency is high for the first time, and specific volume metric density is extra-high, the low ideal next-generation lithium-ion electric of production cost
Pond negative material, specific volume metric density is maintained at 85% or more after recycling 300 weeks, can be applied individually to any extra-high specific volume metric density and reach
3600mAh/g, for the first time coulombic efficiency up to 90% or more high-quality negative material.
Specific implementation mode
With reference to specific embodiment, the present invention is made more comprehensively, careful general introduction, but protection scope of the present invention is simultaneously
It is not limited to following specific examples.
Embodiment 1：By micron order Si particle powders, size d50 weighs 10g and is added to the NO containing Ag ions in 0.8 μm
In-electrolyte solution, evenly dispersed 30min is emulsified, is separated by solid-liquid separation by high speed centrifugation, obtains the granular powder of relatively dry
End uniformly mixes 30min by multidimensional efficient ball mill and is packed into quartz material boat with size d50 in about 1 μm of asphalt powder 10g
In, into vacuum horizontal heating furnace, under Ar gas shields, carbonization cladding is carried out, carburizing temperature is set as 1100 DEG C, constant temperature
2h is naturally cooling to room temperature taking-up, obtains 17g carbon coatings in the composite material of micron order Si particle surfaces, then by composite material
It is added in a concentration of 20% HF solution and emulsifies etching, performed etching to being coated on the Si inside carbon, synchronous punching is cut
Cut, time control in 3~after five minutes, be quickly separated by solid-liquid separation, cleaned, it is dry, obtain silicon-carbon composite cathode material 11.2g.
It is 4.2g through calculating Si contents, carbon content is about 7g, and the volume ratio of silicon-carbon is 36%：64% carbon coating is three inside simple substance Si
Dimension space honeycomb structure negative material.
By obtained silicon-carbon clad composite material respectively with conductive agent acetylene black, binder PVDF is by mass percentage
79:10:11 mixing, wherein above-mentioned silicon-carbon clad composite material 2.37g is weighed, acetylene black 0.3g, PVDF0.33g, with NMP (1-
Formaldehyde -2- pyrroles cyclic ketones) the above mixture is tuned into slurry, it is coated uniformly on copper foil, 110 DEG C are dried in vacuo 20 hours, system
Obtain experiment pole piece, using lithium piece as counter electrode, EC (ethyl carbonate ester)+DMC (dimethyl carbon of electrolyte 1mol/L, LIPEC
Acid esters) volume ratio 1:1 solution, diaphragm are Le/gard2400 films, and CR2025 button electricity is dressed up in the glove box full of argon gas
Pond, made electrode was through first week 0.05C multiplying power current density, second week to the 8th week 0.1C multiplying power current density, and the 9th
Zhou Zhi is measured for 28 weeks using 0.2C rate battery density, refers to table 1, and it is 1638.5706mAh/ to obtain first discharge specific capacity
G, charge specific capacity 1408.6213mAh/g, coulombic efficiency is about 85.96% for the first time, charging capacity conservation rate after 28 weeks cycles
It is 98.83%, almost decaying is seldom.
Embodiment 2
By 1 obtained silicon-carbon clad composite material of embodiment compared with conventional artificial plumbago negative pole material with 1:4
Ratio uniformly mixes 20min using efficient multidimensional ball mill, and CR2025 type button cell pole pieces are made with 1 same procedure of embodiment
It measures 28 weeks and recycles with 1 same period method of same embodiment, refer to table 2, first discharge specific capacity 607.7128mAh/g fills
Electric specific capacity is 556.7529mAh/g, and coulombic efficiency is up to charge specific capacity conservation rate after 91.5%, 28 week cycle for the first time
98.72%, almost decaying is seldom.
Embodiment 3
It is 1.3 μm by micron order Si particle powders d50, weighs 10g, be added to the SO containing Cu4 2-In solion, add
It is 0.01mol/L to enter the solution concentration after Si particle powders, emulsifies evenly dispersed 30min, and disperseing solid-liquid by high speed centrifugation obtains
It to the powder particle of relatively dry, is then added in the graphene oxide solution of a concentration of 0.2wt/g, stirs 1.5h, drying is put
Enter in quartz boat, into vacuum horizontal heating furnace, under the protection of Ar gases, is warming up to 900 DEG C and carries out charing cladding, constant temperature
2h is naturally cooling to room temperature taking-up, obtains the composite material that 10.8g graphene carbon-coatings are coated on micron order Si particle surfaces, then
Composite material is add to deionized water evenly dispersed 30min, is added HF solution, a concentration of 3%, internal etching is carried out to Si
Punch-cuts, time control were quickly separated by solid-liquid separation in 6~8 minutes, were cleaned, dry, obtained graphene layer carbon silicon composite wood
Expect 5.5g, is about 5.3g through calculating Si contents, graphene layer carbon is about 0.7g, obtains silicon：Graphene layer carbon is about 86：17 stone
Black alkene layer carbon coating makes in the negative material of simple substance Si interior three-dimensional spatial cell shape structures, the method with embodiment 1
CR2025 types button cell and with 1 phase same multiplying current density method of embodiment, measures 28 weeks loop-around datas, refers to table 3, for the first time
Specific discharge capacity is 3580.7215mAh/g, and initial charge specific capacity is 3150.6228mAh/g, and coulombic efficiency is about for the first time
Conservation rate is recycled after 87.98%, 28 weeks in 97.8%, almost decaying is seldom.
Embodiment 4
By micron order Si particles with embodiment 1, difference is to be added to containing AgNO3 -In electrolyte solution, other
With 1 same procedure of embodiment.CR2025 button cells are made by 1 same procedure of embodiment, by 1 phase same multiplying electric current of embodiment
Under density conditions, the specific volume that discharges for the first time is tested, fills specific capacity for the first time, coulomb time efficiency and 28 weeks loop tests, obtain for the first time
As a result it is that, referring to chart 4, first discharge specific capacity 1208.5765mAh/g, initial charge specific capacity is 882.2608mAh/
g.Coulombic efficiency is about 73% for the first time, and after 28 weeks cycles, charge specific capacity is about 222.6656mAh/g, and decaying almost approaches
80%.
According to embodiment 1,2,3,4 as can be seen that after metal ion solution processing is added to micron silicon particle surface, together
After metal ion treatment is not added, same method etching is entirely different come the cycle performance method for producing button cell test,
By be added metal ion perform etching plus hole after silicon-carbon composite cathode material, cycle performance is outstanding, not by metal from
Sub- solution treatment, the due capacity almost all of silicon attenuates after cycle 20 weeks.
The test data of 1-embodiment of table 1:
The test data of 2-embodiment of table 2:
The test data of 3-embodiment of table 3：
The test data of 4-embodiment of table 4：
Claims (7)
1. the method that micron order Si prepares three-dimensional honeycomb shape nanosizing Si, it is characterised in that：Include the following steps：
(1) the simple substance Si particle powders for being 0.2~5 μm by D50, are added in electrolytic etching of metal matter solution, after simple substance Si is added
Electrolytic etching of metal matter solution concentration is 0.005~5mol/L, solid-to-liquid ratio is 3~38%：97~62%, using ultrasonic wave or mulser
Or magnetic wave vibration it is evenly dispersed, jitter time be 10~300min, make the attached sorption metal ion of simple substance Si particle surfaces, using from
The heart detaches or compression filtering or vacuum filtration or spray drying or evaporation drying, obtain the attached suction in relatively dry, surface have metal from
The micron order Si granular materials of son；
(2) the Si granular materials for obtaining step (1) carries out carbon coating, obtains carbon-coated Si granular materials；
(3) the carbon-coated Si granular materials that step (2) obtains is added in deionized water solution or ethanol solution, control is solid
Liquor ratio is 3~40%：97~60%, evenly dispersed to carry out, jitter time is 10~300min；
(4) dispersion that step (3) obtains is added in the mixed solution of HF solution or HF and HO-and is mixed, HF therein
A concentration of 3~30%, HO- a concentration of 0.1~10%, incorporation time are 5~500min, and the etching of Si granular materials is beaten in realization
Hole；
(5) the Si granular materials of step (4) etching punching is dried by natural subsidence or centrifugation or evaporation or spraying is dry
Dry separation solid-liquid obtains relatively dry, Si particle surfaces by the Si particle powder materials of carbon-coated cellular nano.
2. the method that micron order Si according to claim 1 prepares three-dimensional honeycomb shape nanosizing Si, it is characterised in that：It is described
Carbon coating be to make carbon coating form carbon coating layer in Si particle surfaces through high temperature carbonization by more than one the substance that carbonizes,
Carbonization temperature is 380~1380 DEG C, and carbonization time is 1~12 hour；Or the carbon coating is carbonizing by more than one
Gas generates the carbide formation carbon coating layer for being deposited on Si particle surfaces, the carbon coating layer and micron by Pintsch process
The volume ratio of grade Si particles is 3~95%：97~5%.
3. the method that micron order Si according to claim 2 prepares three-dimensional honeycomb shape nanosizing Si, it is characterised in that：It is described
The substance that carbonizes be：High molecular polymer phenolic resin, polypropylene be fine, epoxide resin, graphene oxide, pitch, sucrose, shallow lake
Powder, glucose；It is described can charring gas be：Methane, acetylene, ethylene, ethane, the third ethylene, propane.
4. the method that micron order Si according to claim 2 prepares three-dimensional honeycomb shape nanosizing Si, it is characterised in that：It is described
Carbonization temperature be 750~1150 DEG C, carbonization time be 1.5~6 hours.
5. the method that micron order Si according to claim 1 prepares three-dimensional honeycomb shape nanosizing Si, it is characterised in that：It is described
It is 98~99.9999% coarse material that simple substance Si, which is with purity, passes through dry ball milling or wet ball grinding or efficient multidimensional ball milling
Or the simple substance Si particle powder materials that the D50 of the mechanical ball mill method processing of resonance ball milling is 0.2~5 μm, or utilize half
The simple substance Si particle powder materials that conductor IC circular wafers or the D50 of photovoltaic cell processing are 0.2~5 μm.
6. the method that micron order Si according to claim 1 prepares three-dimensional honeycomb shape nanosizing Si, it is characterised in that：It is described
Electrolytic etching of metal matter solution be metal NO3- solion or metal SO4 2-Solion or metal OH-ion solution.
7. prepared with the methods for preparing three-dimensional honeycomb shape nanosizing Si of the micron order Si described in claim 1-6 any one three
Tie up the purposes of cellular nano Si, it is characterised in that：Can be individually used for extra-high capacity than lithium ion battery negative material, or
By natural graphite, artificial graphite, interphase microballoon graphitization, hard carbon, soft carbon negative material more than one material with it is described
Three-dimensional honeycomb shape nanosizing Si be uniformly mixed be applied to lithium ion battery in, produce high power capacity than negative material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105189352A (en) * | 2013-09-02 | 2015-12-23 | 株式会社Lg化学 | Porous silicon based particles, method for preparing same and anode active material comprising same |
| CN107248570A (en) * | 2017-05-26 | 2017-10-13 | 华中科技大学 | A kind of core shell structure Si/C materials, preparation method and application |
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- 2018-03-03 CN CN201810176501.3A patent/CN108390018A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105189352A (en) * | 2013-09-02 | 2015-12-23 | 株式会社Lg化学 | Porous silicon based particles, method for preparing same and anode active material comprising same |
| CN107248570A (en) * | 2017-05-26 | 2017-10-13 | 华中科技大学 | A kind of core shell structure Si/C materials, preparation method and application |
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