CN107425186A - A kind of lithium ion battery negative material - Google Patents

A kind of lithium ion battery negative material Download PDF

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Publication number
CN107425186A
CN107425186A CN201710594180.4A CN201710594180A CN107425186A CN 107425186 A CN107425186 A CN 107425186A CN 201710594180 A CN201710594180 A CN 201710594180A CN 107425186 A CN107425186 A CN 107425186A
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China
Prior art keywords
lithium ion
ion battery
battery negative
suspension
solution
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CN201710594180.4A
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Chinese (zh)
Inventor
张丽鹏
穆洁尘
张小杰
张宇飞
于作洋
陈金
王瑗忠
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Shandong University of Technology
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Shandong University of Technology
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Priority to CN201710594180.4A priority Critical patent/CN107425186A/en
Publication of CN107425186A publication Critical patent/CN107425186A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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

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  • 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)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of lithium ion battery negative material, its preparation method is：Surface modification treatment is carried out to Si particles using surfactant so that Mg (OH)2Easily it is coated on nano Si powder surface；Si particles are dissolved in stirring and ultrasound generation mixing suspension in cetyl benzenesulfonic acid bromination aqueous ammonium first, then magnesium nitrate, urea and glucose are added in above-mentioned suspension and stir 3h；To stir complete suspension pour into ptfe autoclave place into homogeneous reactor set gradient temperature react first 160 DEG C reaction 3h, then 180 DEG C reaction 6h, solid material is washed with deionized and in 40 DEG C of dry 12h after the complete cooling of question response；Composite produced by the present invention has high conductivity and constitutionally stable carbon material is shell, and the introducing of graphene can not only alleviate collapsing for electrode material structure, and largely improve the ion and electronic conductivity of material.

Description

A kind of lithium ion battery negative material
Technical field
The present invention relates to technical field of composite materials, specifically a kind of lithium ion battery negative material.
Background technology
The research of negative material plays decisive role to lithium ion battery, and the lithium metal studied earliest has lithium battery Larger safety problem, Li dendrite easily occurs during iterative cycles, pierce through barrier film, cause short circuit, or even blast on fire.Carbon materials The application of material solves the safety problem of metal lithium electrode, but specific capacity to be present low (372mAh/g) for carbon material[1], fill first The deficiencies of discharging efficiency is low, and organic solvent is embedded in altogether.In recent years, people have started the non-carbon negative material to other height ratio capacities Research, such as alloy, silicon substrate, transition metal oxide and titanium base material.The costs of wherein silicon materials is low, security performance is high And there is higher theoretical specific capacity (4200mAh/g)[2,3], by extensive concern both domestic and external.But in charge and discharge process, bear Larger volumetric expansion easily occurs for pole Si, causes material efflorescence to be reunited, electrical contact is lost between particle and conductive network, so as to Internal resistance is set to increase rapidly, chemical property is decayed rapidly[2-4]。
To solve the problems of silicon based anode material, domestic and foreign scholars have carried out substantial amounts of research and discovery.At present Main research concentrates on following two aspects：First, prepare nanostructured silica-base material, such as nanosphere or nano wire.Chen Jun Deng[5]Use NH4Br aoxidizes NaSi, is prepared for nest like silicon nanosphere, under 2A/g current densities, the circle of circulation 50, and reversible specific capacity For 1000mAh/g；Su Fabing etc.[6]Porous spongy Si materials are prepared for the method for electrochemical etching silicon chip, in 1A/g electric currents The lower circle of circulation 1000, reversible specific capacity reach 750mAh/g.Second, prepare silicon and the compound of other materials, mainly including silicon- Metallic composite and silico-carbo composite.Wherein, the carbon in silico-carbo composite has good Li insertion extraction work(in itself Can, Stability Analysis of Structures and wide material sources, it can be played a supporting role in Si electrode material dilatancies；In addition, carbon has There is satisfactory electrical conductivity, the electric conductivity of electrode is can effectively improve after incorporation.Separately there is researcher[7]With SBA-15 points of magnesiothermic reduction Sub- sieve series into mesoporous silicon, with carbon it is compound after, 100 circles are circulated under 4.2A/g current densities, capacity is able to maintain that in 1500mAh/ g；Tang etc.[8]The Si/ carbon that hot preparation core-shell type is synchronously total to magnesiothermic reduction titanium dioxide Gui nanospheres and glucose compound is received Rice electrode material, circulates 200 circles under 1A/g current density, and reversible specific capacity reaches 1018mAh/g.It can be seen that silicon-based anode Although the research of material has certain development, improve its cycle performance applied to high specific energy electrokinetic cell and still need to further depth Enter research.
The content of the invention
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of lithium ion battery negative material- The Si/C of yolk-eggshell shape is composite porous, and it is shell to have high conductivity and constitutionally stable carbon material, is wrapped in nanometer Si particles, and suitable three-dimensional pore space around it be present, in electrode reaction Si expansion and shrinking occur in the small of surrounding In region so that electrode structure is stable.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of lithium ion battery negative material, its preparation method comprise the following steps that：
(1) Si/Mg (OH) is prepared2/ C-material：
Surface modification treatment is carried out to Si particles using surfactant so that Mg (OH)2Easily it is coated on nano Si powder Last surface；Si particles are dissolved in stirring and ultrasound generation mixing suspension in cetyl benzenesulfonic acid bromination aqueous ammonium first, Magnesium nitrate, urea and glucose are added in above-mentioned suspension again and stir 3h；Complete suspension will be stirred and pour into polytetrafluoro Placed into ethylene reaction kettle in homogeneous reactor and set gradient temperature to react first 160 DEG C of reaction 3h, then 180 DEG C of reaction 6h.Treat Solid material is washed with deionized and in 40 DEG C of dry 12h after having reacted cooling；
(2) it is composite porous to prepare yolk-eggshell Si/C：
In order to prepare pore structure, Mg (OH)2The hydrochloric acid solution that pH is about 2.3 is used to remove using as sacrifice layer, will be upper The material for stating preparation is added in 2L hydrochloric acid solution and stirs 3 days, then filtration washing and dries 4h at 60 DEG C and obtains precursor, so Precursor is put into tube furnace logical nitrogen afterwards and calcines 3h at 350 DEG C；
(3) graphene coated yolk-shell Si/C is composite porous：
Graphene oxide, dialysis and freeze-drying are prepared by improved Hummers methods to obtain rufous graphite oxide Alkene film, a certain amount of graphene oxide is completely dissolved in deionized water to form solution A, then, passes through ultrasonic disperse By a certain amount of porous C/Si powder dissolving in deionized water to form solution B, then, solution B is added in solution A, It is stirred at room temperature 30 minutes, is then freeze-dried, sample is in tube furnace in N2(99.999%) enter in atmosphere at 400 DEG C One step is carbonized 4 hours, and the Si/C composites of graphene modified are made.
As a further improvement on the present invention, in the step 1, selected coating material is cetyl benzenesulfonic acid Ammonium bromide, concentration 0.05-0.07mol/L.
As a further improvement on the present invention, in the step 1, magnesium nitrate, urea, the mol ratio of glucose are 1:3:2.
After said structure, beneficial effects of the present invention are：
First, carbon material has good electric conductivity in itself, coats the Si of high power capacity, improves the monolithic conductive of material.
2nd, carbon material Stability Analysis of Structures, there is substantial amounts of hole around nano Si particle, the meeting production for being Si in charge and discharge process Raw huge Volume Changes have reserved space, prevent material matrix from destroying, improve the long circulating performance of material.
3rd, the diffusion of electrolyte is beneficial to around Si in hole, substantially reduces the migration path of lithium ion, lithium ion Effective high speed deintercalation, so as to reach the target for improving high rate capability.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the Technology Roadmap of the present invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with accompanying drawing and specific implementation Mode, the present invention will be described in further detail.It should be appreciated that embodiment described herein is only explaining this Invention, is not intended to limit the present invention.
Embodiment：
A kind of preparation method of lithium ion battery negative material is：
(1) Si/Mg (OH) is prepared2/ C-material
Surface modification treatment is carried out to Si particles using surfactant (cetyl benzenesulfonic acid ammonium bromide) so that Mg (OH)2Easily it is coated on nano Si powder surface.Si particles are dissolved in cetyl benzenesulfonic acid bromination aqueous ammonium first and being stirred Mix and ultrasound generates mixing suspension, then magnesium nitrate, urea and glucose are added in above-mentioned suspension and stir 3h.Wherein, Si, magnesium nitrate and urea mol ratio are 1:1:3.Complete suspension will be stirred pour into ptfe autoclave and place into Gradient temperature is set to react first 160 DEG C of reaction 3h, then 180 DEG C of reaction 6h in homogeneous reactor.By solid after the complete cooling of question response Material is washed with deionized and in 40 DEG C of dry 12h.
(2) it is composite porous to prepare yolk-eggshell Si/C
In order to prepare pore structure, Mg (OH)2The hydrochloric acid solution that pH is about 2.3 is used to remove using as sacrifice layer.Will be upper The material for stating preparation is added in 2L hydrochloric acid solution and stirs 3 days, then filtration washing and dries 4h at 60 DEG C and obtains precursor.So Precursor is put into tube furnace logical nitrogen afterwards and calcines 3h at 350 DEG C.
(3) graphene coated yolk-shell Si/C is composite porous
Graphene oxide, dialysis and freeze-drying are prepared by improved Hummers methods to obtain rufous graphite oxide Alkene film.A certain amount of graphene oxide is completely dissolved in deionized water to form solution A.Then, ultrasonic disperse is passed through A certain amount of porous C/Si powder is dissolved in deionized water to form solution B.Then, solution B is added in solution A, It is stirred at room temperature 30 minutes.Then it is freeze-dried, sample is in tube furnace in N2(99.999%) enter in atmosphere at 400 DEG C One step is carbonized 4 hours, and the Si/C composites of graphene modified are made.
Present embodiment selects surface modifier first, and the surface of nano Si is modified, makes nano Si particle uniform Disperse and be advantageous to Mg (OH)2Cladding.Handled using hydro-thermal method gradient temperature and coated in nano Si particle surface priority Mg(OH)2And amorphous carbon layer.Then hydrochloric acid is reused by Mg (OH)2Remove to form duct between Si particles and carbon-coating.Most Graphene coated yolk-composite porous preparation process of shell Si/C and material are used afterwards.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling Change is included in the present invention.Any reference in claim should not be considered as to the involved claim of limitation.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art It is appreciated that other embodiment.

Claims (3)

  1. A kind of 1. lithium ion battery negative material, it is characterised in that：Its preparation method comprises the following steps that：
    (1) Si/Mg (OH) is prepared2/ C-material：
    Surface modification treatment is carried out to Si particles using surfactant so that Mg (OH)2Easily it is coated on nano Si powder table Face；Si particles are dissolved in stirring and ultrasound generation mixing suspension in cetyl benzenesulfonic acid bromination aqueous ammonium first, then will Magnesium nitrate, urea and glucose are added in above-mentioned suspension and stir 3h；Complete suspension will be stirred and pour into polytetrafluoroethylene (PTFE) Placed into reactor in homogeneous reactor and set gradient temperature to react first 160 DEG C of reaction 3h, then 180 DEG C of reaction 6h, question response Solid material is washed with deionized and in 40 DEG C of dry 12h after complete cooling；
    (2) it is composite porous to prepare yolk-eggshell Si/C：
    In order to prepare pore structure, Mg (OH)2The hydrochloric acid solution that pH is about 2.3 is used to remove using as sacrifice layer, by above-mentioned preparation Material be added in 2L hydrochloric acid solution and stir 3 days, then filtration washing and dry 4h at 60 DEG C and obtain precursor, then will before Body is put into tube furnace logical nitrogen and calcines 3h at 350 DEG C；
    (3) graphene coated yolk-shell Si/C is composite porous：
    Graphene oxide is prepared by improved Hummers methods, dialysis and freeze-drying are thin to obtain rufous graphene oxide Film, a certain amount of graphene oxide is completely dissolved in deionized water to form solution A, then, by ultrasonic disperse by one Quantitative porous C/Si powder dissolving then, solution B is added in solution A, in room in deionized water to form solution B The lower stirring of temperature 30 minutes, is then freeze-dried, sample is in tube furnace in N2(99.999%) it is further at 400 DEG C in atmosphere Carbonization 4 hours, the Si/C composites of graphene modified are made.
  2. A kind of 2. lithium ion battery negative material according to claim 1, it is characterised in that：It is selected in the step (1) Coating material is cetyl benzenesulfonic acid ammonium bromide, concentration 0.05-0.07mol/L.
  3. A kind of 3. lithium ion battery negative material according to claim 1, it is characterised in that：In the step (1), nitric acid Magnesium, urea, the mol ratio of glucose are 1:3:2.
CN201710594180.4A 2017-07-20 2017-07-20 A kind of lithium ion battery negative material Pending CN107425186A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113130849A (en) * 2021-04-09 2021-07-16 珠海冠宇电池股份有限公司 Composite silicon material and lithium ion battery
CN113363458A (en) * 2021-06-03 2021-09-07 开封平煤新型炭材料科技有限公司 Preparation method of silicon-carbon negative electrode material
CN114188665A (en) * 2021-12-06 2022-03-15 江苏厚生新能源科技有限公司 High-flame-retardance and high-mechanical-strength lithium ion battery diaphragm and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130344392A1 (en) * 2011-06-30 2013-12-26 Northwestern University Crumpled graphene-encapsulated nanostructures and lithium ion battery anodes made therefrom
CN106711419A (en) * 2017-01-05 2017-05-24 山东理工大学 Core-shell NiO/C porous composite lithium ion battery negative electrode material
CN106784709A (en) * 2016-12-28 2017-05-31 山东理工大学 A kind of preparation method of lithium ion battery negative material-cobalt-based composite
CN106941164A (en) * 2017-04-11 2017-07-11 东南大学 A kind of preparation method of lithium ion battery negative nucleocapsid clad structure material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130344392A1 (en) * 2011-06-30 2013-12-26 Northwestern University Crumpled graphene-encapsulated nanostructures and lithium ion battery anodes made therefrom
CN106784709A (en) * 2016-12-28 2017-05-31 山东理工大学 A kind of preparation method of lithium ion battery negative material-cobalt-based composite
CN106711419A (en) * 2017-01-05 2017-05-24 山东理工大学 Core-shell NiO/C porous composite lithium ion battery negative electrode material
CN106941164A (en) * 2017-04-11 2017-07-11 东南大学 A kind of preparation method of lithium ion battery negative nucleocapsid clad structure material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113130849A (en) * 2021-04-09 2021-07-16 珠海冠宇电池股份有限公司 Composite silicon material and lithium ion battery
CN113130849B (en) * 2021-04-09 2022-07-08 珠海冠宇电池股份有限公司 Composite silicon material and lithium ion battery
CN113363458A (en) * 2021-06-03 2021-09-07 开封平煤新型炭材料科技有限公司 Preparation method of silicon-carbon negative electrode material
CN113363458B (en) * 2021-06-03 2022-11-15 开封平煤新型炭材料科技有限公司 Preparation method of silicon-carbon negative electrode material
CN114188665A (en) * 2021-12-06 2022-03-15 江苏厚生新能源科技有限公司 High-flame-retardance and high-mechanical-strength lithium ion battery diaphragm and preparation method thereof
CN114188665B (en) * 2021-12-06 2023-09-29 江苏厚生新能源科技有限公司 Lithium ion battery diaphragm with high flame retardance and high mechanical strength and preparation method thereof

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Application publication date: 20171201