CN109698327A - Lithium ion battery negative material - Google Patents

Lithium ion battery negative material Download PDF

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Publication number
CN109698327A
CN109698327A CN201710997022.3A CN201710997022A CN109698327A CN 109698327 A CN109698327 A CN 109698327A CN 201710997022 A CN201710997022 A CN 201710997022A CN 109698327 A CN109698327 A CN 109698327A
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silicon nitride
lithium ion
beta phase
ion battery
phase silicon
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CN109698327B (en
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魏汝超
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SUPER ENERGY MATERIALS Inc
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SUPER ENERGY MATERIALS Inc
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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
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • 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)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of lithium ion battery negative material, silicon nitride structure of the negative electrode material based on beta phase silicon nitride, includes the beta phase silicon nitride of 50wt% or more in the silicon nitride.Beta phase silicon nitride is the hexagonal system structure of stratiform, because having lamellar character, lithium ion insertion is promoted to go out to be easy with embedding, reduce because lithium ion can not be successfully it is embedding go out due to generate Li dendrite (Lithium Dendrites) structure, and because of charge and discharge procedure structure dimensionally stable, the decline of capacitance caused by material fragmentation, disintegration can be greatly reduced, to improve cycle life.Disclosed in this invention beta phase silicon nitride, its chemical formula is β-Si3Nx, wherein 1≤x≤4, due to low nitrogen-atoms weight percent, so beta phase silicon nitride (β-Si3Nx) has unstable dangling bonds, unsaturated bond and other unpaired bonds, the activity and capacitance of negative electrode material can be improved.

Description

Lithium ion battery negative material
Technical field
The present invention provides a kind of lithium ion battery negative material, refers in particular to a kind of beta phase silicon nitride including unsaturated bond Lithium ion battery negative material.
Background technique
Lithium ion battery largely uses on electronic product, but with the development of science and technology, can no longer meet Gao Rong The demand of battery is measured, silicon based anode material has high capacitance characteristic, is the highest cathode of capacitance now up to 4200mAh/g Material, but there are lithium ion insertion with it is embedding go out after, the shortcomings that caused negative electrode material fragmentation and dusting, to solve the above problems, Many researchs are modified and are modified from ingredient and structure to silica-base material.The wherein modification on composition is silicon and one or more The atom of a non-silicon is mixed with physics, chemical bonded refractory forms compound or alloy form；And the modification in structure, have nanosizing, Modification on nucleocapsid structure, fibre structure and bond structures change or exterior appearance.
The problems such as prior art has patent proposition, improves negative electrode material volume expansion and cycle life using silicon nitride, With nucleocapsid structure or fiber membrane structure type, negative electrode material is coated, can inhibit volume expansion and passivating film (solid Electrolyte interphase, SEI) generate [1-5].Another part patent proposes the negative electrode materials such as silicon nitride and graphite After mixing, being sintered, compound negative electrode material is prepared, it is strong with the thermal conductivity, electric conductivity, construction machine that increase the negative electrode material Degree destroys the characteristics [6-7] such as ductile strength.Silicon nitride assists primarily as negative electrode material and buffers it in above-mentioned patent With, and the capacitance of lithium ion battery can not be increased, improve cycle life of lithium ion battery effect limitation.
Make silicon nitride with such as column or hollow nanotube-shaped knot from the change of silicon nitride in person using forming technique Structure generates, and reserves surrounding space position, lithium ion insertion can be made to be easy with embedding volume expansion out, reaching has stable cycle life [8-10], but it still has the defect in structural strength, lithium ion insertion with it is embedding go out react under, volume expansion and contraction, meeting because Stress concentrates on negative electrode material and current collection contact level, and negative electrode material top position, and has the generation of the problems such as rupture, dusting, Lead to the decline for reducing negative electrode material capacitance and cycle life.
Though being mentioned in the prior art with crystalline silicon nitride phase structure as negative electrode material [11-12], all without spy Indescribably go out its crystal structure of silicon nitride composition and its proportional region, α phase silicon nitride is trigonal system structure, and lattice is stood Body barrier is greater than the layer structure of beta phase silicon nitride, influence lithium ion insertion with it is embedding go out, be unfavorable for the capacitance of negative electrode material and follow The ring service life.
In conclusion how to avoid the volume expansion of negative electrode material and promote the activity and electricity of lithium ion battery negative material Capacity will be an important and anxious to be resolved project.
Biliographic data:
[1]JP4171904(B2)
[2]CN106531986(A)
[3]KR101422648(B1)
[4]CN106532010(A)
[5]CN105047920(B)
[6]CN104030273(B)
[7]CN102017246(A)
[8]JP2010073571(A)
[9]JP5210162(B2)
[10]CN105047920(B)
[11]JP3713900(B2)
[12]EP2287946(A1)。
Summary of the invention
To solve the above problems, the present invention provides a kind of lithium ion battery negative material, the negative electrode material includes nitridation Silicon includes the beta phase silicon nitride of 50wt% or more in the silicon nitride, and the chemical formula of the beta phase silicon nitride is β-Si3Nx, wherein x Range be 1≤x≤4.
The weight percent of its nitrogen atom content of beta phase silicon nitride is between 15%~40% and includes suspension Key, unsaturated bond or unpaired key, partial size is between 0.01~50 μm.
The silicon nitride of the negative electrode material can simultaneously be combined with graphite, graphene, carbon fiber or pitch prill.
Negative electrode material of the present invention by the stratiform hexagonal system structure of beta phase silicon nitride, provide lithium ion battery charging with When electric discharge, lithium ion insertion and embedding channel out, and due to stable structure, low-expansion coefficient and excellent chemical stabilization, suppression The insertion of cathode material lithium ion processed and it is embedding go out caused by expansion, shrink, and generation situations such as lead to fragmentation and dusting, raising follow The ring service life, and to control nitrogen content, promote dangling bond to generate, the activity and capacitance of Lai Zengjia negative electrode material reach master of the present invention Syllabus.
Detailed description of the invention
Fig. 1 is beta phase silicon nitride schematic diagram containing dangling bonds；
Fig. 2 is beta phase silicon nitride and the negative electrode material structural schematic diagram that graphite particle mixes；
Fig. 3 is that beta phase silicon nitride and graphene mix negative electrode material structural schematic diagram；
Fig. 4 is the negative electrode material structural schematic diagram that beta phase silicon nitride and carbon fiber mix；
Fig. 5 is the nucleocapsid structure negative electrode material structural schematic diagram of beta phase silicon nitride.
Symbol description
101 nitrogen-atoms, 102 silicon atom
103 dangling bonds, 201 silicon nitride
202 graphite particle, 203 graphene
204 carbon fiber, 205 carbonaceous hard shell
Specific embodiment
The negative electrode material of lithium ion battery, which includes the silicon nitride structure based on beta phase silicon nitride, described It include the beta phase silicon nitride of 50wt% or more in 201 structure of silicon nitride, Fig. 1 is to be bonded by nitrogen-atoms 101 and silicon atom 102 Beta phase silicon nitride crystal structure schematic diagram, chemical formula be β-Si3Nx, wherein x range is 1≤x≤4, it is characterized in that institute State beta phase silicon nitride (β-Si3Nx), there is one or more dangling bonds 103, unsaturated bond or unpaired bond, cathode material can be increased The activity and capacitance of material, and beta phase silicon nitride is the layer structure of hexagonal crystal system, it is possible to provide lithium ion insertion and embedding stabilization out Channel, to maintain the lithium ion battery good circulation service life.The negative electrode material of the tool silicon nitride can individually be used in lithium ion The preparation of cell negative electrode material can also be used in mixed way with other negative electrode materials, be prepared into a kind of compound lithium ion battery Cathode.The beta phase silicon nitride included in the silicon nitride structure the more more can provide more lithium ion insertion and it is embedding out Stable channel, effectively to promote the lithium ion battery good circulation service life.Under the preferable situation, beta phase silicon nitride is in silicon nitride knot More than 70wt% in structure, when beta phase silicon nitride ratio shared in silicon nitride structure is higher, expression α phase silicon nitride is in silicon nitride Shared ratio is lower in structure, it is possible to prevente effectively from α phase silicon nitride negatively affects lithium ion battery bring.
Silicon nitride (Si3N4) chemical stability, resistance to compression, low-expansion coefficient, the corrosion-resistant intensity that have had is high, hardness The characteristics such as height, good mechanical property, at normal temperatures and pressures, general silicon nitride have α phase and coexist with beta phase silicon nitride ingredient, and α phase nitrogenizes The crystal structure of silicon is trigonal system structure, and space group P31c is detrimental to lithium ion insertion due to its crystal structure characteristic With it is embedding go out；Beta phase silicon nitride is hexagonal system structure, and the space group of beta phase silicon nitride is P63/m, lattice constant a= 0.7608nm, c=0.2911nm, α=β=90 °, γ=120 ° [13] arrange because beta phase silicon nitride is bonded, make its crystal structure For stable laminated structure.The ionic radius of lithium ion is 0.076nm, can by the stabilization stratiform spacing of beta phase silicon nitride, lithium from When sub- battery charge and discharge, insertion goes out to be easy with embedding, and since beta phase silicon nitride has good resistance to compression and lower expansion Coefficient reduces volume because expanding, shrinking, causes negative electrode material to be crushed, disintegration, lithium can be substantially improved in caused loss of capacitance The charge and discharge efficiency and cycle life that ion battery uses.Wherein weight percent shared by beta phase silicon nitride is greater than α phase and nitrogenizes Weight percent shared by silicon, that is, weight percent shared by beta phase silicon nitride will reach 50wt% or more, can just highlight β phase and nitrogenize Silicon structure characteristic and benefit.
Its chemical formula of beta phase silicon nitride included in negative electrode material of the present invention is β-Si3Nx, wherein x range is 1≤x≤4, The nitrogen content of beta phase silicon nitride is mainly controlled using nitrogen source, is prepared the beta phase silicon nitride with low content nitrogen-atoms, is made the β phase Silicon nitride has one or more dangling bonds, unsaturated bond or unpaired bond, makes it have the characteristic of high activity.β phase nitrogenizes The bond intensity of Si-N covalency key of the silicon on c-axis is greater than other adjacent directionkeys knotting strengths [14], therefore dangling bonds are easy It is generated in c-axis with outside direction, for maintenance beta phase silicon nitride crystal structure, the covalent bond of dangling bonds and Si-N can be on adjacent axis It replaces, causes beta phase silicon nitride overall activity to increase, the position of beta phase silicon nitride hangs inside key not only can be in crystal structure Portion can also be random and DYNAMIC DISTRIBUTION in the outer surface of crystal structure, and lithium ion insertion goes out to react with embedding, can be because hanging The characteristic of key, and be easier to carry out, reactive chemistry formula is as follows:Insertion with it is embedding go out The y range of lithium ion is 0≤y≤9, and under the premise of maintaining beta phase silicon nitride architectural characteristic, the nitrogen content of beta phase silicon nitride is reduced, Linkage content is hung to increase, it is embedded more with embedding lithium ion quantity out, make the negative electrode material of the beta phase silicon nitride comprising dangling bonds Characteristic with high-capacitance.
However, nitrogen content is to influence lithium ion battery negative material capacitor and active Chief amongst, if its nitrogen-atoms When content is more than 40% weight percent, suspension linkage content is decreased obviously, and leads to the reduction of activity and capacitance；And when nitrogen is former When sub- content is lower than 15% weight percent, although its dangling bonds increasing proportion, crystal phase nitrogen is formed since its nitrogen content is lower than The nitrogen content of SiClx will be unable to maintain negative electrode material structural strength, and be biased to the N doping of silica-base material, be formed without the silicon for determining phase Nitrogen compound structure will lead to the use cycle life and capacitance fall-off of lithium ion battery, therefore nitrogen content will affect suspension The quantity of key, and the content of dangling bonds be the present invention in influence lithium ion battery negative material activity with capacitance it is main because Element.
It is 0.01~50 μm that the partial size of the beta phase silicon nitride of tool dangling bonds of the invention, which selects optimum range, if grain diameter Too small, because SEI is generated, electrolyte consumption increases, and capacitance is caused to fail, if partial size is too big, coating can be uneven, influences cathode Material total quality.
Illustrate practical application of the invention for multiple embodiments below.
First embodiment, to contain high-content (such as 70wt% or more) beta phase silicon nitride (β-Si3Nx) silicon nitride 201 be Main negative electrode material is prepared into negative electrode material using its dangling bonds 103 and its characteristic of crystal layer structure.
Second embodiment, as shown in Fig. 2, physically being mixed with silicon nitride 201 and graphite particle 202, preparation is negative Pole material, if 201 content of beta phase silicon nitride is more, graphite is the function for increasing cathode overall conductivity, and capacitance is with β phase nitrogen The capacitance of SiClx 201 is presented；If 202 content of graphite particle is more, beta phase silicon nitride 201, which has, increases by 202 capacitor of graphite particle The effect of amount and stable structure, the modification on ingredient is done to 202 negative electrode material of graphite particle.
3rd embodiment is prepared as negative electrode material, and graphite as shown in figure 3, mixing with silicon nitride 201 and graphene 203 Alkene 203 be stratiform and reticular structure, increase negative electrode material electric conductivity the advantages of.
Fourth embodiment is prepared as negative electrode material, carbon after mixing as shown in figure 4, silicon nitride 201 and carbon fiber 204 mix Fiber 204 in negative electrode material, can be strengthened the intensity of silicon nitride structure and increase the conduction of whole negative electrode material with skeleton pattern Property.
5th embodiment, as shown in figure 5, silicon nitride 201, is sintered, in 201 structural outside layers shape of silicon nitride after mixing with pitch prill It is nucleocapsid structure, to increase the structural strength and overall conductivity of negative electrode material at one layer of carbonaceous hard shell 205.
Negative electrode material of the present invention is based on beta phase silicon nitride, the stratiform hexagonal crystal tying of advantage combination beta phase silicon nitride Structure provides lithium ion battery in charge and discharge, lithium ion insertion with it is embedding go out channel, and due to stable structure, low swollen Swollen coefficient and excellent chemical stabilization, inhibit cathode material lithium ion insertion and it is embedding go out caused by expansion, shrink, and cause to collapse It is broken to be generated with situations such as dusting, cycle life is improved, and to control nitrogen content, dangling bond is promoted to generate, Lai Zengjia negative electrode material Activity and capacitance, reach main purpose of the present invention.
Embodiment described above and/or embodiment are only the preferred embodiments to illustrate to realize the technology of the present invention And/or embodiment, not the embodiment of the technology of the present invention is made any form of restriction, any those skilled in the art Member changes or is revised as other equivalent when can make a little in the range for not departing from technological means disclosed in the content of present invention Embodiment, but still should be regarded as and the substantially identical technology or embodiment of the present invention.
Biliographic data:
[13]J.Am.Ceram.Soc.,83[10]2449 54(2000)
[14]Chin.Phys.Sin.2006,55(7),3585-3589。

Claims (9)

1. a kind of lithium ion battery negative material, which is characterized in that including silicon nitride, the beta phase silicon nitride content of the silicon nitride Up to 50wt% or more, the chemical formula of the beta phase silicon nitride is β-Si3Nx, and wherein the range of x is 1≤x≤4.
2. lithium ion battery negative material as described in claim 1, which is characterized in that the nitrogen-atoms of the beta phase silicon nitride contains The weight percent of amount is between 15%~40%.
3. lithium ion battery negative material as described in claim 1, which is characterized in that the beta phase silicon nitride accounts for silicon nitride knot The weight percent of structure is 70% or more.
4. lithium ion battery negative material as described in claim 1, which is characterized in that the beta phase silicon nitride includes suspension Key, unsaturated bond or unpaired key.
5. lithium ion battery negative material as described in claim 1, which is characterized in that the partial size of the beta phase silicon nitride between Between 0.01~50 μm.
6. the lithium ion battery negative material as described in any in claim 1 to 5, which is characterized in that further comprise graphite Particle, the graphite particle are physically mixed with the silicon nitride.
7. the lithium ion battery negative material as described in any in claim 1 to 5, which is characterized in that further comprise graphite Alkene, the graphene with the silicon nitride to mix.
8. the lithium ion battery negative material as described in any in claim 1 to 5, which is characterized in that further comprise carbon fiber Dimension, the carbon fiber forms skeleton after mixing with the silicon nitride, to strengthen the structural strength of silicon nitride.
9. the lithium ion battery negative material as described in any in claim 1 to 5, which is characterized in that it further comprise pitch prill, The silicon nitride is sintered after mixing with pitch prill, forms one layer of carbonaceous hard shell in the nitridation outer silicon.
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Cited By (1)

* Cited by examiner, † Cited by third party
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