CN106252651A - A kind of lithium ion battery porous composite negative pole material and preparation method thereof - Google Patents
A kind of lithium ion battery porous composite negative pole material and preparation method thereof Download PDFInfo
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- CN106252651A CN106252651A CN201610936369.2A CN201610936369A CN106252651A CN 106252651 A CN106252651 A CN 106252651A CN 201610936369 A CN201610936369 A CN 201610936369A CN 106252651 A CN106252651 A CN 106252651A
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- 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
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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
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- H—ELECTRICITY
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of lithium ion battery porous composite negative pole material and preparation method thereof.This composite negative pole material is a kind of composite with loose structure, and it is with the transition metal oxide M of loose structurexOyFor skeleton, hole is filled with nano-silicon.The preparation method of this composite negative pole material, including: transition metal salt and nano-silicon are scattered in solvent, stir and load reactor；Transition metal carbonate presoma is obtained through co-precipitation or spray drying；Described transition metal carbonate presoma is calcined at 400 1000 DEG C, prepares the composite with loose structure.This porous composite negative pole material provides the headspace that silica-base material expands so that integral material volumetric expansion during embedding de-lithium is less, and then improves its cycle performance, and synthesis technique is simple, is suitable to industrialized production.
Description
Technical field
The present invention relates to battery material field, specifically, relate to a kind of lithium ion battery porous composite negative pole composite wood
Material, its preparation method and application.
Background technology
Lithium ion battery because having running voltage height, service life cycle length, memory-less effect, self discharge is little, environment is friendly
The advantage such as good, has been widely used in portable type electronic product and electric automobile.People are to current business-like lithium-ion electric
Pond proposes higher requirement, it is desirable to it has higher energy density, higher power density.And lithium ion positive and negative pole material is
One of central factor that energy density promotes.Current business-like negative material is mainly graphite material, but its theoretical capacity
Only 372mAh/g, seriously constrains the lifting of lithium ion battery integral energy density.Therefore, exploitation specific capacity is high, performance is excellent
Different lithium ion battery negative material has important practical significance to promoting energy density.
Metal-oxide and silica-base material (theoretical capacity 4200mAh/g) are to study the hottest lithium ion battery negative at present
Material, wherein the current capacity of silica-base material is the highest, can be divided into pure silicon material and the sub-silicon materials of oxidation.But silica-base material is generally deposited
Problem be during embedding lithium takes off lithium, volumetric expansion is very big, and then whole battery pole piece expands, and ultimately results in circulating battery
Lost efficacy.Therefore, the expansion solving silica-base material is the key point of research at present.
In order to solve the problems referred to above, the most many researcheres all design with optimizing in the modification being devoted to silicium cathode material,
The problems referred to above solving silica-base material generally have three class methods:
First kind method is by silicon nanorize.Because along with the reduction of silicon grain, silicon can be reduced to a certain extent
Change in volume, reduces electrode interior stress.Typical example such as Kang Kibum et al. utilizes chemical vapour deposition technique, SiH4Gas
Body goes out Si nano wire by Au catalysis in rustless steel (SUS) superficial growth, prepares Si/NW/SUS electrode, and with simple silicon
Powder carries out the contrast of chemical property, finds that the capacity first of Si nano wire reaches 4000mAh/g, no better than the theory of silicon
Capacity, and circulate the coulombic efficiency of 50 times between 98%-99%, capacity maintains more than 1500mAh/g；Charge and discharge process
The nano wire of middle silicon is at silicon wafer phase and Li22Si5There is reversible transition between crystalline phase, maintain the stability of electrode, improve following of battery
Ring performance (Kang Kibum, et al.Maximum Li storage in Si nanowires for the high
capacity three dimensional Li-ion battery.Appl.Phys.Lett.,96:053110.2010)。
US2008/0280207A1 discloses the continuous film surface at the silicon grain composition of nano-scale, and deposition of carbon nanotubes manufactures lithium
Ion battery cathode material.The total defect of above-mentioned silicon nanorize is that nano material is easily reunited in cyclic process, not enough so that
The performance improvement of battery is to practical, and process is complicated, and manufacturing cost is high, is unsuitable for large-scale production.
Equations of The Second Kind method is to prepare the composite of siliceous/carbon.It is most commonly that and uses carbon cladding or the mode system of deposition
Standby silicon/carbon composite.The specific capacity of silicon can be caused to have declined although adding carbon, but still be much higher than the specific volume of carbon itself
Amount, can be as the ideal substitute of carbon negative electrode material of lithium ion cell.Such as CN101153358A discloses high molecular polymerization
Thing, silica flour and graphite powder mixing, ball milling, and high temperature cabonization processes a kind of lithium ion battery negative material of preparation in noble gas
Material.CN101210119A discloses and utilizes conducting polymer coated Si particle to form lithium ion battery negative material method, should
Material contains silicon particle and is coated on the clad of silicon particle surface, and wherein, described clad is conducting polymer.This kind of method
Total defect be that silicon particle that it is used needs preparation especially, some uses substantial amounts of organic solvent, dispersant or bonding
Agent, major part method is the most just to complete and need, through break process, to destroy the clad structure of product, and these are all
Increase production cost and bring great inconvenience to industrialized production simultaneously, be unfavorable for the industrialization of lithium ion silicon based anode material.
3rd class method is silicon and the material such as metal reacts, and generates silicon alloy or adds other metal components.On the one hand gold
Belong to material and can improve the electric conductivity of silicon materials so that all of silicon all plays the effect of active material at electrochemistry removal lithium embedded,
On the other hand metal material can disperse and buffer silicon materials change in volume institute during removal lithium embedded as " cushioning frame "
The internal stress produced, makes silicon composite have good cycle performance.Typical example such as CN101643864A, it passes through will
Silicon and metal mixing and ball milling by a certain percentage form multielement silicon alloy, more multiple with graphite mixing and ball milling formation multielement silicon alloy/carbon
Condensation material, as lithium ion battery negative.CN1242502C discloses employing two-step sintering method, first prepares silico-aluminum, then will
Organic polymer Pintsch process, processes under the conditions of elevated-temperature seal after adding graphite powder and obtains lithium ion battery negative material aluminum silicon
Alloy/carbon composite.CN104617278A discloses a kind of nano-silicon metallic composite, and it is relative to nanometer by content
Silicon metallic composite is the elemental silicon of 5-75mol% and comprises compound and the silicon that metallic element, metallic element and silicon are formed
Oxygen compound and simple substance carbon composition, it is with the mixture of silicon dioxide, metal and carbon as raw material, passes through molten salt electrolysis method
Make silicon dioxide be electrochemically reduced to nano-silicon and be formed in situ nano-silicon metallic composite.The major defect of this kind of method is
Silicon alloy forming process is complicated, and alloy structure difficulty controls, and production cost is high, and the electrochemical properties of material is unstable.Due to these
Silicon alloy does not make full use of the cooperative effect of various metals, although these alloy materials are relative to their electrochemistry of pure silicon
Performance has greatly improved, but the improvement of cycle performance is the most very limited.
It is simple that oxide cathode material has preparation method, and the feature that theoretical specific capacity is high, is the 2-3 of graphite material capacity
Times, become one of a new generation promising candidate of negative material.Some scholars is had to have studied the compound negative pole of MnO Yu CNT at present
Material, it shows higher specific capacity and cycle performance (Xiaofei Sun, et al., The composite sphere
of manganese oxide and carbon nanotubes as a prospective anode material for
Lithium-ion batteries.Journal of Power Sources, 255:163-169,2014), also there is document to report
The Ni of porous0.14Mn0.86O1.43The preparation of microsphere negative material, its specific capacity after circulating 150 weeks remains in that 553mAh/
G, shows good cycle performance (Zhong Ma, et al., Porous Ni0.14Mn0.86O1.43hollow
microspheres as high-performing anodes for lithium-ion batteries.Journal of
Power Sources 291:156-162,2015).CN102339996A also proposed MnOxThe synthesis road of spherical porous material
Line, prepares the MnO with ductxMaterial, its specific capacity is far above the carbon element negative material commonly used at present.
CN103227321A discloses a kind of manganese series oxides MnOxAnd Fe2O3Composite nano powder material, it uses hydrothermal method to close
One-tenth obtains.
Also having part research at present is the negative material being prepared as metal oxide composite having loose structure.Allusion quotation
The example of type such as CN103050679A discloses a kind of spherical hollow porous MnO/C composite, described spherical hollow porous
MnO/C composite is with natural frustule as carbon source and template, by material with carbon element, hollow loose structure and manganese monoxide nano-particle
Three effectively combines.CN102324501A discloses a kind of Si/CuO with loose structurex/ C composite (0≤x
≤ 1), it is with the silicon of loose structure as matrix, CuOxIn granule embedded hole, the carbon of different shape is uniformly distributed in silica-base material
Surface and hole wall on, by using organosilicon, industrial silicon and halohydrocarbons reaction Technology, in conjunction with carbon composite modified modification skill
Art, prepares porous Si/CuOx/ C composite be used as lithium ion battery negative material, improve silicon based anode material the most no
Reversible capacity, stable circulation performance.The major defect of this kind of method be silica-base material during embedding lithium takes off lithium, volumetric expansion is still
Relatively big, it is unfavorable for improving the cycle performance of battery.
Generally there is silica-base material during embedding lithium takes off lithium in these preparation methods reported above, volumetric expansion is relatively big,
The problems such as cost of material height, complicated process of preparation, cause the electrochemistry of lithium ion battery can meet business demand, it is impossible to
Industrialization.
Summary of the invention
For the deficiencies in the prior art, the present invention is by using coprecipitation or spray drying method, with transiting metal oxidation
Thing MxOyIt is raw material with silica-base material, prepares the M with loose structurexOy/ Si composite is used as lithium ion battery negative
Material, not only reduces the bulk expansion of negative material, and due to MxOyIt is respectively provided with high capacity, Liang Zhefa with silica-base material
After waving synergism, substantially increase the specific capacity of negative material, stable circulation performance, and solve silicon based anode material production
The problems such as cost height, complex process and industrialized production difficulty.
An object of the present invention is to provide a kind of novel lithium ion battery negative material.
According to the present invention, the composite material having porous structure of described lithium ion battery negative material, with the mistake of loose structure
Cross metal-oxide MxOyFor skeleton, hole is filled with nano-silicon.
According to the present invention, described lithium ion battery negative material has porous or microcellular structure, and nano-silicon was filled in
Cross metal-oxide MxOyAmong the porous of negative material, not only achieve the dispersion of nano material, additionally provide silicon substrate simultaneously
The headspace that material expands so that integral material volumetric expansion during embedding de-lithium is the least, and both play synergism, enter
And improve its cycle performance.
According to the present invention, described transition metal oxide MxOy, x span is 0 ＜ x≤2, y span be 0 ＜ y≤
3, M is any one or the mixture of at least two in Ni, Co, Mn, Ti, Cu.Described transition metal oxide MxOyCan select
From NiO, Ni2O3、CoO、Co2O3、MnO、Mn2O3、TiO、TiO2、Ti2O3、Cu、Cu2Any one or at least two in O, CuO
Mixture, the Typical non-limiting example of described mixture is: NiO and Ni2O3Mixture, Ni2O3With the mixture of CoO,
Co2O3With the mixture of MnO, TiO2With the mixture of CuO, Co2O3, MnO and Mn2O3Mixture, TiO2、Ti2O3, Cu and Cu2O
Mixture, CoO, Co2O3、MnO、Mn2O3、TiO、TiO2、Ti2O3、Cu、Cu2The mixture of O and CuO, preferably NiO,
Ni2O3、CoO、Co2O3、MnO、Mn2O3In any one or the mixture of at least two.
According to the present invention, in described lithium ion battery negative material, described hole size and pattern are uniform.In described hole
Value particle diameter is 1.0-45.0 μm, such as, can be 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5.0 μm, 6.0 μm, 8.0 μm, 10.0 μ
m、11.0μm、12.0μm、15.0μm、18.0μm、20.0μm、21.5μm、23.0μm、25.0μm、28.0μm、30.0μm、33.5μ
M, 35.0 μm, 38.0 μm, 41.0 μm, 45.0 μm, preferably 5.0-25.0 μm, the structure-controllable in described hole is adjustable, it is also possible to logical
Later process the structure to hole, size, pattern, distribution and porosity to be finely adjusted.
According to the present invention, described nano-silicon is crystalline silicon, amorphous silicon, in silicon oxide, silicon monoxide any one or
The mixture of at least two, the Typical non-limiting example of described mixture is: crystalline silicon and the mixture of silicon oxide, amorphous
Silicon and the mixture of the mixture of silicon oxide, silicon oxide and silicon monoxide, the mixing of amorphous silicon, silicon oxide and silicon monoxide
Any one or the mixture of at least two in thing, preferably crystalline silicon, silicon oxide, silicon monoxide.
According to the present invention, described transition metal oxide MxOyControllable with silicon nanoparticle size.Described transition metal
Oxide MxOyGranular size can be nanoscale or micron order, the median particle diameter of described nano-silicon is 20.0-300.0nm, example
As being 20.0 μm, 22.0 μm, 25.0 μm, 30.0 μm, 35.0 μm, 45.0 μm, 52.0 μm, 60.0 μm, 63.0 μm, 68.0 μ
m、71.0μm、78.0μm、90.0μm、100.5μm、130.0μm、180.0μm、200.0μm、235.0μm、250.0μm、260.0μ
M, 270.0 μm, 280.0 μm, 300.0 μm, preferably 25.0-250.0nm, more preferably 30.0-200.0nm, described in receive
The hole size of rice silicon is finely adjusted also by post processing.
According to the present invention, in described composite, described transition metal oxide MxOyShared molar percentage is 30-
99%, the most described transition metal oxide MxOyThe molar percentage accounting for described composite total amount is 30-99%, the most permissible
30%, 32%, 35%, 40%, 45%, 50%, 62%, 65%, 70%, 75%, 80%, 82%, 85%, 87%, 90%,
95%, 98% or 99%, preferably 50-80%；It is 1-that described nano-silicon accounts for the molar percentage of described composite total amount
70%, can be such as 1%, 2%, 5%, 8%, 9%, 10%, 12%, 15%, 18%, 20%, 23%, 25%, 28%,
30%, 32%, 35%, 38%, 40%, 50%, 60%, 65% or 70%, preferably 20-50%.
The two of the purpose of the present invention also reside in the preparation method providing a kind of novel lithium ion battery negative material, bag
Include step as follows:
(1) transition metal salt and nano-silicon are scattered in solvent, stir and load reactor；
(2) transition metal carbonate presoma is obtained through co-precipitation or spray drying in the reactor；
(3) described transition metal carbonate presoma is calcined at 400-1000 DEG C, prepares and has loose structure
Composite.
According to the present invention, described preparation method has been used coprecipitation or spray drying method, be successfully prepared have many
Hole or the M of microcellular structurexOy/ Si composite, by transition metal salt in this composite and the reaction of nano-silicon so that whole
The volumetric expansion during embedding de-lithium of body material is the least, improves the cycle performance of lithium ion battery.
According to the present invention, only by transition metal salt and the ratio of nano-silicon in set-up procedure (1), it is not necessary to change it
Its technological parameter, just can obtain the product of following two type:
The product of one of them is the lithium ion battery negative material as described in one of the object of the invention, with loose structure
Transition metal oxide MxOyFor skeleton, hole is filled with nano-silicon；The concrete preparation method of this lithium ion battery negative material
Comprise the following steps that
(1) transition metal salt and nano-silicon are scattered in solvent, stir and load reactor；
(2) transition metal carbonate presoma is obtained through co-precipitation or spray drying in the reactor；
(3) described transition metal carbonate presoma is calcined at 400-1000 DEG C, prepares and has loose structure
Composite.
Another has the lithium ion battery negative material of loose structure, with the nano-silicon of loose structure as skeleton, and hole
Gap is filled with transition metal oxide MxOy；The concrete preparation method of this lithium ion battery negative material comprises the following steps that
(1) transition metal salt and nano-silicon are scattered in solvent, stir and load reactor；
(2) transition metal carbonate presoma is obtained through co-precipitation or spray drying in the reactor；
(3) described transition metal carbonate presoma is calcined at 400-1000 DEG C, prepares and has loose structure
Composite.
The content limited further below is all be applicable to the preparation method of above-mentioned both products.
According to the present invention, step (1) described transition metal salt is in the nitrate of transition metal, sulfate, chlorate
Any one or the mixture of at least two, preferably Ni (NO3)2、NiSO4、Ni(ClO3)2、Co(NO3)2、CoSO4、Co
(ClO3)2、Mn(NO3)2、MnSO4、Mn(ClO3)2、Ti(NO3)2、TiSO4、Ti(ClO3)2、Cu(NO3)2、CuSO4、Cu(ClO3)2
In any one or the mixture of at least two.
According to the present invention, the transition metal ions contained in step (1) described transition metal salt is Ni2+、Ni3+、Co2+、
Co3+、Mn2+、Mn3+、Ti2+、Ti3+、Cu2+In any one or the mixture of at least two.
According to the present invention, step (1) described nano-silicon is crystalline silicon, amorphous silicon, any in silicon oxide, silicon monoxide
Any one or at least two in a kind of or the mixture of at least two, preferably crystalline silicon, silicon oxide, silicon monoxide mixed
Compound；The median particle diameter of described nano-silicon is 20.0-300.0nm, more preferably 25.0-250.0nm, more preferably
30.0-200.0nm。
According to the present invention, dispersant is used in step (1) described dispersion, and described dispersant is sodium tripolyphosphate, hexa metaphosphoric acid
Sodium, sodium pyrophosphate, triethyl group hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol, cellulose derivative, polyacrylamide, Gu
Your glue, fatty acid polyethylene glycol ester, cetyl trimethylammonium bromide, Polyethylene Glycol are to isooctyl phenyl ether, polyacrylic acid, poly-
In vinylpyrrolidone, polyoxyethylene sorbitan monooleate dehydration, p-ethylbenzoic acid, Polyetherimide any one or
The mixture of at least two.
According to the present invention, step (1) described solvent is water or organic solvent, and described organic solvent is appointing in alcohol, ketone, ether
Anticipate a kind of or mixture of at least two.
According to the present invention, step (1) described reactor is vacuum drying oven, batch-type furnace, rotary furnace, roller kilns, pushed bat kiln, tubular type
Any one in stove.
According to the present invention, precipitant is used in step (2) described co-precipitation, and described precipitant is carbonate and/or bicarbonate
Salt, preferably ammonium carbonate and/or ammonium hydrogen carbonate.
According to the present invention, step (3) described calcining is carried out under protective atmosphere, and described protective atmosphere is nitrogen, helium
Any one or the mixture of at least two in gas, neon, argon, Krypton, xenon；The temperature of described calcining is 500-800
DEG C, preferably 600-750 DEG C；The heating rate of described calcining is 1.0-20.0 DEG C/min, preferably 5.0-15.0 DEG C/min；Institute
The time stating calcining is 4-48h, preferably 5-30h.
The method of co-precipitation of the present invention or spray drying is all the known method of art, art technology
Personnel know these methods, and can select concrete and suitable method according to actual conditions, and reach intended target setting.Base
Being known method in it, the present invention no longer goes to live in the household of one's in-laws on getting married with regard to the concrete technology step of described coprecipitation or spray drying method and technological process
State.
Present invention also offers a kind of lithium ion battery, it uses has the composite of loose structure as the present invention is above-mentioned
As lithium ion battery negative material.
The present invention is by with transition metal oxide MxOySpherical honeycombed grain is carrier, embedding nano silica-base material, is formed
MxOy/ Si composite, MxOyLoose structure provides space for based particles volumetric expansion in charge and discharge process, and makes material
Material bulk expansion goes to zero；And MxOyBeing respectively provided with high capacity with silica-base material, both pass through synergism, can make composite wood
The specific capacity of material is at least over 1000mAh/g, and then improves the cycle performance of lithium ion battery.
Compared with prior art, beneficial effects of the present invention is embodied in:
1, the invention provides a kind of new Modification design method of composite cathode material for lithium ion cell；
2, the loose structure of the present invention alleviates nano silicon material in charge and discharge process because volumetric expansion and contraction produce
Mechanical stress, eliminate bulk effect, the bulk expansion of material goes to zero；
3, in the loose structure of the present invention, transition metal oxide MxOyIt is respectively provided with high capacity with nano silicon material, passes through
Coprecipitation or spray drying method, both can play synergism, make the specific capacity theory at least over graphite of composite
Capacity, and then improve the cycle performance of lithium ion battery；
4, as the production technology that silicon-based anode material of lithium-ion battery is novel, there is low production cost, technique
Simply, pollution-free, the large-scale production advantage such as easily.
Accompanying drawing explanation
Fig. 1 is the structural representation of the composite of embodiment 1 preparation；
Fig. 2 is the scanning electron microscopic picture of the composite of embodiment 1 preparation；
Fig. 3 is the charging curve of the composite of embodiment 1,2,3 and comparative example 1 preparation；
Fig. 4 is the cyclic curve of the composite of embodiment 1,2,3 and comparative example 1 preparation；
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example only help understands the present invention, is not construed as the concrete restriction to the present invention.
Following example are with transition metal salt and silicon nanoparticle as raw material, are obtained by coprecipitation or spray drying method
After presoma, through the composite of the loose structure of calcining preparation, and carry out electrochemical property test.Nano-silicon used
Grain and transition metal salt are commercially produced product.
Embodiment 1
The preparation method employing following two step of the composite of loose structure:
(1) by Mn (NO3)2It is dispersed in water by sodium tripolyphosphate with the silica flour that median particle diameter is 20.0nm, stirs 1h,
By spray pyrolysis, the product that will obtain, lotion, dry, it is thus achieved that presoma；
(2) this presoma is at batch-type furnace with the programming rate of 5 DEG C/min, and under nitrogen atmosphere, 700 DEG C are incubated 4 hours, preparation
Obtain the composite with loose structure；In this composite, it is 25% that silica flour accounts for the molar percentage of composite, manganese
It is 75% that oxide accounts for the molar percentage of composite.
Embodiment 2
The preparation method employing following two step of the composite of loose structure:
(1) by cobaltous acetate and silicon nanowires that median particle diameter is 100.0nm by sodium lauryl sulphate be scattered in from
In sub-water, stir 3h, be spray-dried, it is thus achieved that presoma；
(2), by presoma in pushed bat kiln, with the programming rate of 10 DEG C/min, under nitrogen atmosphere, 800 DEG C are incubated 6 hours,
Prepare the composite with loose structure；In this composite, silicon nanowires accounts for the molar percentage of composite and is
10%, it is 90% that the oxide of cobalt accounts for the molar percentage of composite.
Embodiment 3
The preparation method employing following two step of the composite of loose structure:
(1) by Ni (NO that mass ratio is 1:1:13)2、Co(NO3)2And MnSO4And the oxygen that median particle diameter is 50.0nm
SiClx is disperseed in aqueous, adds ammonium hydrogen carbonate, stirs 2h, through filtering, washing, dries and obtains presoma；
(2) in rotary furnace, presoma will be obtained, with the programming rate of 15 DEG C/min, 900 DEG C, protect under Krypton atmosphere
Temperature 2 hours, prepares the composite with loose structure；In this composite, silicon monoxide account for composite mole
Percentage ratio is 30%, and it is 70% that nickel, cobalt and Mn oxide account for the molar percentage of composite altogether.
Embodiment 4
The preparation method employing following two step of the composite of loose structure:
(1) by MnSO4Unformed silicon with median particle diameter is 20.0nm, is dispersed in water by sodium tripolyphosphate, stirring
1h, adds sodium carbonate, stirs 6 hours, and washing is filtered, and dries and obtains presoma；
(2) composite precursor will be obtained, in a vacuum furnace the programming rate of 1 DEG C/min, under nitrogen atmosphere, 500 DEG C of calcinings
48 hours, prepare the composite with loose structure；In this composite, unformed silicon accounts for moles the hundred of composite
Proportion by subtraction is 40%, and it is 60% that the oxide of manganese accounts for the molar percentage of composite.
Embodiment 5
The preparation method employing following two step of the composite of loose structure:
(1) by Mn (NO that mass ratio is 2:13)2And NiSO4And silicon nanowires that median particle diameter is 250.0nm and an oxygen
SiClx is scattered in deionized water by cetyl trimethylammonium bromide, stirs 2.5h, adds carbamide, at 60 DEG C, stirs 4
Hour, washing, filter, it is thus achieved that presoma；
(2) presoma will be obtained, in a nitrogen atmosphere, with the programming rate of 20 DEG C/min, forge for 1000 DEG C in tube furnace
Burn 1 hour, prepare the composite with loose structure；In this composite, silicon nanowires and silicon monoxide account for multiple altogether
The molar percentage of condensation material is 70%, and it is 30% that the oxide of manganese and nickel accounts for the molar percentage of composite altogether.
Embodiment 6
The preparation method employing following two step of the composite of loose structure:
(1) by Cu (NiO3)2It is scattered in by sodium lauryl sulphate with the silicon monoxide that median particle diameter is 100.0nm
In ionized water, stir 3h, be spray-dried, it is thus achieved that presoma；
(2), by presoma in pushed bat kiln, with the programming rate of 10 DEG C/min, under nitrogen atmosphere, 800 DEG C are incubated 6 hours,
Prepare the composite with loose structure；In this composite, silicon monoxide accounts for the molar percentage of composite and is
50%, it is 50% that the oxide of copper accounts for the molar percentage of composite.
Comparative example 1
Material proportion design and calcination condition and process identical with embodiment 1, differ only in following steps.
(1) MnO and the silica flour that median particle diameter is 20.0nm are dispersed in water by sodium tripolyphosphate, stir 1h, volatilization
Fall moisture content, it is thus achieved that composite；In this composite, it is 40% that silica flour accounts for the molar percentage of composite, and MnO accounts for composite wood
The molar percentage of material is 60%.
Comparative example 2
Material proportion design and calcination condition embodiment 3 are identical, differ only in following steps.
(1) it is the NiCO of 1:1:1 by mass ratio3、CoCO3And MnCO3And the silicon monoxide that median particle diameter is 50.0nm mixes
Close uniformly；In rotary furnace, with the programming rate of 15 DEG C/min, 900 DEG C, be incubated 2 hours under Krypton atmosphere, prepare multiple
Condensation material；In this composite, it is 30% that silicon monoxide accounts for the molar percentage of composite, and nickel, cobalt and Mn oxide account for altogether
The molar percentage of composite is 70%.
Chemical property is evaluated: the silicon based composite material of above-mentioned preparation is carried out chemical property evaluation.Battery makes, electricity
Chemical property test is as follows: the mass ratio of porous anode material, acetylene black and PVDF (Kynoar) is 80:10:10,
By porous anode material and acetylene black mix homogeneously, (PVDF is prepare to be subsequently adding PVDF (Kynoar)
The PVDF/NMP solution of 0.02g/mL, NMP is N-Methyl pyrrolidone) solution, be coated on Copper Foil, in vacuum drying oven in
120 DEG C are vacuum dried 24 hours, take the disk of a diameter of 19 centimetres as working electrode, and lithium metal is to electrode, and electrolyte is
LiPF6/EC-DMC-EMC (volume ratio 1:1:1), is assembled into two electrode simulated batteries in full Ar glove box.Charging/discharging voltage
Scope is 2.0-0.01V, and charging and discharging currents density is 100mA/g (0.5C).Electrochemical property test the results are shown in Table 1.
Table 1 electrochemical property test result
Test result shows: the method using the present invention, it is ensured that each component is uniformly dispersed under liquid phase, after heat treatment,
Form that loose structure, effectively suppression produce stress and the material structure that causes destroys, thus improve material cyclical stability and
Capacity performance and first efficiency.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention have to rely on above-mentioned in detail
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a composite with loose structure, it is characterised in that with the transition metal oxide M of loose structurexOyFor bone
Frame, is filled with nano-silicon in hole.
Composite the most according to claim 1, it is characterised in that described transition metal oxide MxOy, x span
Being 0 ＜ x≤3, y span is 0 ＜ y≤4, and M is any one or the mixture of at least two in Ni, Co, Mn, Ti, Cu；
Described transition metal oxide MxOyMore preferably NiO, CoO, Co2O3、MnO、Mn2O3、Mn3O4、TiO2、Ti2O3、
Cu、Cu2Any one or the mixture of at least two, most preferably NiO, CoO, CuO, MnO, Mn in O, CuO2O3In appoint
Anticipate a kind of or mixture of at least two.
Composite the most according to claim 1 and 2, it is characterised in that the median particle diameter in described hole is 1.0-45.0 μm,
It is preferably 5.0-25.0 μm；
Preferably, described transition metal oxide MxOyThe molar percentage accounting for described composite total amount is 30-99%, preferably
For 50-80%, it is 1-70%, preferably 20-50% that described nano-silicon accounts for the molar percentage of described composite total amount.
4. according to the composite one of claim 1-3 Suo Shu, it is characterised in that described nano-silicon is crystalline silicon, amorphous
Silicon, any one or the mixture of at least two, preferably crystalline silicon, silicon oxide, silicon monoxide in silicon oxide, silicon monoxide
In any one or the mixture of at least two；
Preferably, the median particle diameter of described nano-silicon is 20.0-300.0nm, preferably 25.0-250.0nm, more preferably
30.0-200.0nm。
5. the method preparing the composite with loose structure, it is characterised in that comprise the following steps that
(1) transition metal salt and nano-silicon are scattered in solvent, stir and load reactor；
(2) transition metal carbonate presoma is obtained through co-precipitation or spray drying in the reactor；
(3) described transition metal carbonate presoma is calcined at 400-1000 DEG C, prepares and has the compound of loose structure
Material.
Method the most according to claim 5, it is characterised in that described transition metal salt is the nitrate of transition metal, sulfur
Any one or the mixture of at least two, preferably Ni (NO in hydrochlorate, chlorate3)2、NiSO4、Ni(ClO3)2、Co
(NO3)2、CoSO4、Co(ClO3)2、Mn(NO3)2、MnSO4、Mn(ClO3)2、Ti(NO3)2、TiSO4、Ti(ClO3)2、Cu(NO3)2、
CuSO4、Cu(ClO3)2In any one or the mixture of at least two；
Preferably, the transition metal ions contained in described transition metal salt is Ni2+、Ni3+、Co2+、Co3+、Mn2+、Mn3+、Ti2+、
Ti3+、Cu2+In any one or the mixture of at least two；
Preferably, described nano-silicon is crystalline silicon, amorphous silicon, any one or at least two in silicon oxide, silicon monoxide
Mixture, preferably any one in crystalline silicon, silicon oxide, silicon monoxide or the mixture of at least two；
Preferably, the median particle diameter of described nano-silicon is 20.0-300.0nm, more preferably 25.0-250.0nm, more preferably
For 30.0-200.0nm.
7. according to the method described in claim 5 or 6, it is characterised in that dispersant is used in step (1) described dispersion, described point
Powder be sodium tripolyphosphate, sodium hexameta phosphate, sodium pyrophosphate, triethyl group hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol,
Cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, cetyl trimethylammonium bromide, Polyethylene Glycol
To isooctyl phenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate dehydration, to ethylamino benzonitrile
Acid, any one or the mixture of at least two in Polyetherimide；
Preferably, described solvent is water or organic solvent, described organic solvent be in alcohol, ketone, ether any one or at least two
The mixture planted；
Preferably, any one during described reactor is vacuum drying oven, batch-type furnace, rotary furnace, roller kilns, pushed bat kiln, tube furnace；
Preferably, precipitant is used in step (2) described co-precipitation, and described precipitant is carbonate and/or bicarbonate, is preferably
Ammonium carbonate and/or ammonium hydrogen carbonate.
8. according to the method one of claim 5-7 Suo Shu, it is characterised in that step (3) described calcining is under protective atmosphere
Carrying out, described protective atmosphere is the mixed of any one or at least two in nitrogen, helium, neon, argon, Krypton, xenon
Compound；
Preferably, the temperature of described calcining is 500-800 DEG C, preferably 600-750 DEG C；
Preferably, the heating rate of described calcining is 1.0-20.0 DEG C/min, preferably 5.0-15.0 DEG C/min；
Preferably, the time of described calcining is 4-48h, preferably 5-30h.
9. according to the method one of claim 5-8 Suo Shu, it is characterised in that described method comprises the following steps that
(1) by transition metal salt and nano-silicon by dispersant in water or organic solvent, load reaction after stirring 1-4h
Device；
(2) add carbonate and/or bicarbonate, stirring in the reactor, obtain transition metal carbonate forerunner through co-precipitation
Body；
(3) described transition metal carbonate presoma 400-1000 DEG C, calcine 4-48h under protective atmosphere, prepare tool
There is the composite of loose structure.
10. a lithium ion battery, it is characterised in that use and there is as described in one of claim 1-4 the compound of loose structure
Material is used as lithium ion battery negative material.
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| CN108574090A (en) * | 2018-03-13 | 2018-09-25 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN110289400A (en) * | 2019-05-27 | 2019-09-27 | 四川创能新能源材料有限公司 | A kind of dispersing method of nano-silicon |
| CN111370674A (en) * | 2020-03-24 | 2020-07-03 | 江苏厚生新能源科技有限公司 | Low-expansion metal lithium negative electrode, preparation method thereof and lithium battery |
| CN113497223A (en) * | 2020-04-08 | 2021-10-12 | 广州维思新能源有限公司 | Preparation method of porous carbon layer structure coated with graphene nano-silicon composite material |
| WO2023071393A1 (en) * | 2021-10-28 | 2023-05-04 | 广东邦普循环科技有限公司 | Hollow-spherical-particle negative electrode material with openings, and preparation method therefor and use thereof |
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| CN115117327A (en) * | 2022-08-25 | 2022-09-27 | 溧阳天目先导电池材料科技有限公司 | Low-expansion silicon-based composite material and preparation method and application thereof |
| CN115117327B (en) * | 2022-08-25 | 2022-11-22 | 溧阳天目先导电池材料科技有限公司 | Low-expansion silicon-based composite material and preparation method and application thereof |
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