CN106252651B - A kind of porous composite negative pole material of lithium ion battery and preparation method thereof - Google Patents
A kind of porous composite negative pole material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN106252651B CN106252651B CN201610936369.2A CN201610936369A CN106252651B CN 106252651 B CN106252651 B CN 106252651B CN 201610936369 A CN201610936369 A CN 201610936369A CN 106252651 B CN106252651 B CN 106252651B
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- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 72
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 41
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 19
- -1 transition metal salt Chemical class 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910000299 transition metal carbonate Inorganic materials 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 67
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- 229910052710 silicon Inorganic materials 0.000 claims description 34
- 239000010703 silicon Substances 0.000 claims description 34
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
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- 229910016287 MxOy Inorganic materials 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 15
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- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
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- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 4
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
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- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/485—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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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to porous composite negative pole materials of a kind of lithium ion battery and preparation method thereof.The composite negative pole material is a kind of composite material with porous structure, with the transition metal oxide M of porous structurexOyFor skeleton, nano-silicon is filled in hole.The preparation method of the composite negative pole material, comprising: disperse transition metal salt and nano-silicon in solvent, stir and be packed into reactor；It is co-precipitated or is spray-dried to obtain transition metal carbonate presoma；The transition metal carbonate presoma is calcined at 400-1000 DEG C, and the composite material with porous structure is prepared.The porous composite negative pole material provides the reserved space of silica-base material expansion, so that integral material volume expansion during embedding de- lithium is smaller, and then improves its cycle performance, and synthesis technology is simple, is suitable for industrialized production.
Description
Technical field
The present invention relates to battery material fields, specifically, being related to a kind of porous composite negative pole composite wood of lithium ion battery
Material, preparation method and application.
Background technique
Operating voltage height, service life cycle length, memory-less effect, self discharge is small, environment is friendly because having for lithium ion battery
The advantages that good, it has been widely used in portable electronic product and electric car.People are to current commercialized lithium-ion electric
Pond is put forward higher requirements, it is desirable to which it is with higher energy density, higher power density.And lithium ion positive and negative pole material is
One of the central factor that energy density is promoted.Current commercialized negative electrode material is mainly graphite material, however its theoretical capacity
Only 372mAh/g seriously constrains the promotion 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 energy density is promoted.
Metal oxide and silica-base material (theoretical capacity 4200mAh/g) are the most hot negative electrode of lithium ion battery of current research
Material, wherein the current capacity highest of silica-base material, can be divided into pure silicon material and aoxidize sub- silicon materials.However silica-base material is generally deposited
The problem of be during embedding lithium takes off lithium, volume expansion is very big, and then the expansion of entire battery pole piece, eventually leads to circulating battery
Failure.Therefore, the expansion for solving silica-base material is the key point studied at present.
To solve the above-mentioned problems, at present many researchers all in the modification and optimization design for being dedicated to silicium cathode material,
The above problem for solving silica-base material usually has three classes method:
First kind method is by silicon nanosizing.Because can reduce silicon to a certain extent with the reduction of silicon particle
Volume change reduces electrode interior stress.Typical example such as Kang Kibum et al. utilizes chemical vapour deposition technique, SiH4Gas
Body is catalyzed by Au and on the surface stainless steel (SUS) grows Si nano wire, prepares Si/NW/SUS electrode, and with simple silicon
Powder carries out the comparison of chemical property, and the capacity for the first time of discovery Si nano wire reaches 4000mAh/g, no better than the theory of silicon
Capacity, and 50 coulombic efficiencies are recycled between 98%-99%, capacity maintains 1500mAh/g or more；Charge and discharge process
The nano wire of middle silicon is in silicon wafer phase and Li22Si5Reversible transition occurs between crystal phase, maintains the stability of electrode, improves following for 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 is disclosed on the continuous film surface of the silicon particle composition of nano-scale, and deposition of carbon nanotubes manufactures lithium
Ion battery cathode material.The shared defect of above-mentioned silicon nanosizing is that nano material is easy to reunite in cyclic process, is insufficient to allow
The performance improvement of battery is to functionization, and process is complicated, and manufacturing cost is high, is unsuitable for being mass produced.
Second class method is the composite material for preparing siliceous/carbon.The system most commonly by the way of carbon coating or deposition
Standby silicon/carbon composite.Although carbon, which is added, will lead to the specific volume that the specific capacity of silicon is declined, but still is much higher than carbon itself
Amount, can be used as the ideal substitute of carbon negative electrode material of lithium ion cell.Such as CN101153358A is disclosed high molecular polymerization
Object, silicon powder and graphite powder mixing, ball milling, and a kind of negative electrode of lithium ion battery material is prepared in inert gas high temperature carbonization treatment
Material.CN101210119A is disclosed to be coated silicon particle and forms lithium ion battery negative material method using conducting polymer, should
Material contains silicon particle and the clad for being coated on silicon particle surface, wherein the clad is conducting polymer.Such methods
Shared defect be that used silicon particle needs especially preparation, some use a large amount of organic solvent, dispersing agent or bonding
Agent, most of method are the clad structures that could be completed at high temperature and need to destroy product by break process, these are all
Increase production cost and bring great inconvenience to industrialized production simultaneously, is unfavorable for the industrialization of lithium ion silicon based anode material.
Third class method is that the materials such as silicon and metal react, and generates silicon alloy or adds other metal components.On the one hand gold
Category material can improve the electric conductivity of silicon materials, so that all silicon all plays the role of active material in electrochemistry removal lithium embedded,
Another aspect metal material can be used as " cushioning frame " to disperse and buffer silicon materials volume change institute during removal lithium embedded
The internal stress of generation makes silicon composite have good cycle performance.Typical example such as CN101643864A, pass through by
Silicon and metal are mixed in a certain ratio ball milling and form multielement silicon alloy, then multiple with graphite mixing and ball milling formation multielement silicon alloy/carbon
Condensation material is used as negative electrode of lithium ion battery.CN1242502C is disclosed using two-step sintering method, first prepares silico-aluminum, then will
Organic polymer Pintsch process, be added graphite powder after under the conditions of elevated-temperature seal processing obtain lithium ion battery negative material aluminium silicon
Alloy/carbon composite.CN104617278A discloses a kind of nano-silicon metallic composite, is by content relative to nanometer
The elemental silicon that silicon metallic composite is 5-75mol% and the compound and silicon formed comprising metallic element, metallic element and silicon
Oxygen compound and simple substance carbon composition, are to pass through molten salt electrolysis method using the mixture of silica, metal and carbon as raw material
So that silica is electrochemically reduced to nano-silicon and nano-silicon metallic composite is formed in situ.The major defect of such methods is
Silicon alloy forming process is complicated, and alloy structure is difficult to control, high production cost, and the electrochemical properties of material are unstable.Due to these
Silicon alloy does not make full use of the synergistic 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 still very limited.
Oxide cathode material has preparation method simple, and the high feature of theoretical specific capacity is the 2-3 of graphite material capacity
Times, become one of promising candidate of negative electrode material of new generation.There are some scholars to have studied MnO and CNT compound cathode at present
Material 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 report
Porous Ni0.14Mn0.86O1.43The preparation of microballoon negative electrode material, specific capacity still maintains 553mAh/ after circulation 150 weeks
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, specific capacity are much higher than the carbon negative electrode material being commonly used.
CN103227321A discloses a kind of manganese series oxides MnOxAnd Fe2O3Composite nano powder material, use hydrothermal method to close
At obtaining.
It is at present that metal oxide composite is prepared into the negative electrode material with porous structure there are also part research.Allusion quotation
The example of type such as CN103050679A discloses a kind of porous MnO/C composite material of spherical hollow, and the spherical hollow is porous
MnO/C composite material is using natural frustule as carbon source and template, by carbon material, hollow porous structure and manganese monoxide nano particle
Three is effectively combined together.CN102324501A discloses a kind of Si/CuO with porous structurex/ C composite (0≤x
It≤1), is the CuO using the silicon of porous structure as matrixxIn particle 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 the composite modified modification skill of carbon
Porous Si/CuO is made in artx/ C composite is used as lithium ion battery negative material, improve silicon based anode material for the first time not
Reversible capacity, stable circulation performance.The major defect of such methods is silica-base material during embedding lithium takes off lithium, and volume expansion is still
It is larger, it is unfavorable for improving the cycle performance of battery.
The generally existing silica-base material of these preparation methods reported above during embedding lithium takes off lithium, volume expansion is larger,
The problems such as cost of material is high, preparation process is complicated, causes the electrochemistry of lithium ion battery that can meet business demand, can not
Industrialization.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is by using coprecipitation or spray drying process, with transiting metal oxidation
Object MxOyIt is raw material with silica-base material, the M with porous structure is preparedxOy/ Si composite material is used as negative electrode of lithium ion battery
Material not only reduces the bulk expansion of negative electrode material, and due to MxOyHigh capacity, the two hair are all had with silica-base material
After waving synergistic effect, specific capacity, the stable circulation performance of negative electrode material are substantially increased, and solves silicon based anode material production
At high cost, the problems such as complex process and industrialized production are difficult.
One of the objects of the present invention is to provide a kind of novel lithium ion battery negative materials.
According to the present invention, the composite material having porous structure of the lithium ion battery negative material, with the mistake of porous structure
Cross metal oxide MxOyFor skeleton, nano-silicon is filled in hole.
According to the present invention, the lithium ion battery negative material has porous or microcellular structure, and nano-silicon was filled in
Cross metal oxide MxOyNegative electrode material it is porous among, not only realize the dispersion of nano material, while additionally providing silicon substrate
Expect the reserved space of expansion, so that volume expansion very little of integral material during embedding de- lithium, the two plays synergistic effect, into
And improve its cycle performance.
According to the present invention, the transition metal oxide MxOy, x value range be 0 < x≤2, y value range be 0 < y≤
In 3, M Ni, Co, Mn, Ti, Cu any one or at least two mixture.The transition metal oxide MxOyIt can select
From NiO, Ni2O3、CoO、Co2O3、MnO、Mn2O3、TiO、TiO2、Ti2O3、Cu、Cu2O, any one in CuO or at least two
Mixture, the Typical non-limiting example of the 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 at least two mixture.
According to the present invention, in the lithium ion battery negative material, the hole size and pattern are uniform.In the hole
Being worth partial size 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 the hole is adjustable, can also lead to
Later structure, size, pattern, distribution and the porosity for handling device to hole are finely adjusted.
According to the present invention, the nano-silicon is crystalline silicon, amorphous silicon, in silica, silicon monoxide any one or
At least two mixture, the Typical non-limiting example of the mixture is: the mixture of crystalline silicon and silica, amorphous
The mixture of the mixture of silicon and silica, silica and silicon monoxide, the mixing of amorphous silicon, silica and silicon monoxide
Object, preferably crystalline silicon, silica, in silicon monoxide any one or at least two mixture.
According to the present invention, the transition metal oxide MxOyIt is controllable with silicon nanoparticle size.The transition metal
Oxide MxOyGranular size can be nanoscale or micron order, the median particle diameter of the nano-silicon is 20.0-300.0nm, example
It such as can be 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, further preferably 30.0-200.0nm, it is described to receive
The hole size of rice silicon can be also finely adjusted by post-processing.
According to the present invention, in the composite material, the transition metal oxide MxOyShared molar percentage is 30-
99%, i.e., the described transition metal oxide MxOyThe molar percentage for accounting for the composite material total amount is 30-99%, such as can be with
30%, 32%, 35%, 40%, 45%, 50%, 62%, 65%, 70%, 75%, 80%, 82%, 85%, 87%, 90%,
95%, 98% or 99%, preferably 50-80%；The molar percentage that the nano-silicon accounts for the composite material total amount is 1-
70%, for example, can be 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 second object of the present invention, which also resides in, provides a kind of preparation method of novel lithium ion battery negative material, packet
Include that steps are as follows:
(1) it disperses transition metal salt and nano-silicon in solvent, stir and is packed into reactor；
(2) it is co-precipitated or is spray-dried in the reactor to obtain transition metal carbonate presoma；
(3) the transition metal carbonate presoma is calcined at 400-1000 DEG C, is prepared with porous structure
Composite material.
According to the present invention, coprecipitation or spray drying process have been used in the preparation method, be successfully prepared with more
The M of hole or microcellular structurexOy/ Si composite material, by the reaction of transition metal salt and nano-silicon in the composite material, so that whole
Body material volume expansion very little during embedding de- lithium, improves the cycle performance of lithium ion battery.
According to the present invention, only by adjusting the ratio of both transition metal salt in step (1) and nano-silicon, without changing it
Its technological parameter 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 porous structure
Transition metal oxide MxOyFor skeleton, nano-silicon is filled in hole；The specific preparation method of the lithium ion battery negative material
It comprises the following steps that
(1) it disperses transition metal salt and nano-silicon in solvent, stir and is packed into reactor；
(2) it is co-precipitated or is spray-dried in the reactor to obtain transition metal carbonate presoma；
(3) the transition metal carbonate presoma is calcined at 400-1000 DEG C, is prepared with porous structure
Composite material.
Another lithium ion battery negative material with porous structure, using the nano-silicon of porous structure as skeleton, hole
Transition metal oxide M is filled in gapxOy；The specific preparation method of the lithium ion battery negative material comprises the following steps that
(1) it disperses transition metal salt and nano-silicon in solvent, stir and is packed into reactor；
(2) it is co-precipitated or is spray-dried in the reactor to obtain transition metal carbonate presoma；
(3) the transition metal carbonate presoma is calcined at 400-1000 DEG C, is prepared with porous structure
Composite material.
The content limited further below is suitable for the preparation method of both above-mentioned products.
According to the present invention, step (1) transition metal salt is in the nitrate, sulfate, chlorate of transition metal
Any one or at least two mixture, 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 at least two mixture.
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 at least two mixture.
According to the present invention, step (1) nano-silicon is crystalline silicon, amorphous silicon, any in silica, silicon monoxide
It is a kind of or at least two mixture, preferably crystalline silicon, silica, in silicon monoxide any one or at least two it is mixed
Close object；The median particle diameter of the nano-silicon be 20.0-300.0nm, further preferably 25.0-250.0nm, more preferably
30.0-200.0nm。
According to the present invention, dispersing agent is used in step (1) dispersion, and the dispersing agent is sodium tripolyphosphate, hexa metaphosphoric acid
Sodium, sodium pyrophosphate, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, 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-
Vinylpyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid, in polyetherimide any one or
At least two mixture.
According to the present invention, step (1) solvent is water or organic solvent, and the organic solvent is alcohol, ketone, appointing in ether
It anticipates a kind of or at least two mixtures.
According to the present invention, step (1) reactor is vacuum drying oven, batch-type furnace, rotary furnace, roller kilns, pushed bat kiln, tubular type
Any one in furnace.
According to the present invention, precipitating reagent is used in step (2) co-precipitation, and the precipitating reagent is carbonate and/or bicarbonate
Salt, preferably ammonium carbonate and/or ammonium hydrogen carbonate.
According to the present invention, step (3) calcining carries out under protective atmosphere, and the protective atmosphere is nitrogen, helium
Gas, neon, argon gas, Krypton, in xenon any one or at least two mixture；The temperature of the calcining is 500-800
DEG C, preferably 600-750 DEG C；The heating rate of the calcining be 1.0-20.0 DEG C/min, preferably 5.0-15.0 DEG C/min；Institute
The time for stating calcining is 4-48h, preferably 5-30h.
The method of co-precipitation or spray drying of the present invention is the known method of technical field, art technology
These known methods of personnel, and specific and suitable method can be selected according to actual conditions, and reach expected and set target.Base
It is known method in it, the present invention is no longer superfluous with regard to the specific process step and process flow of the coprecipitation or spray drying process
It states.
The present invention also provides a kind of lithium ion battery, use such as the above-mentioned composite material with porous structure of the present invention
As lithium ion battery negative material.
The present invention passes through with transition metal oxide MxOySpherical honeycombed grain is carrier, and embedding nano silica-base material is formed
MxOy/ Si composite material, MxOyThe volume expansion that porous structure is based particles in charge and discharge process provides space, and makes material
Material bulk expansion goes to zero；And MxOyHigh capacity is all had with silica-base material, the two can make composite wood by synergistic effect
The specific capacity of material improves the cycle performance of lithium ion battery at least over 1000mAh/g.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1, the present invention provides a kind of new Modification design methods of composite cathode material for lithium ion cell；
2, porous structure of the invention alleviates nano silicon material in charge and discharge process because volume expansion and contraction generate
Mechanical stress, eliminate bulk effect, the bulk expansion of material goes to zero；
3, in porous structure of the invention, transition metal oxide MxOyHigh capacity is all had with nano silicon material, is passed through
Coprecipitation or spray drying process, the two can play synergistic effect, make the specific capacity of composite material at least over the theory of graphite
Capacity, and then improve the cycle performance of lithium ion battery；
4, the production technology novel as silicon-based anode material of lithium-ion battery has low production cost, technique
Simply, the advantages that pollution-free, large-scale production is easy.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of composite material prepared by embodiment 1；
Fig. 2 is the scanning electron microscopic picture of composite material prepared by embodiment 1；
Fig. 3 is the charging curve of composite material prepared by embodiment 1,2,3 and comparative example 1；
Fig. 4 is the cyclic curve of composite material prepared by embodiment 1,2,3 and comparative example 1；
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Following embodiment is to be obtained using transition metal salt and silicon nanoparticle as raw material by coprecipitation or spray drying process
To after presoma, the composite material of the porous structure through 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 of the composite material of porous structure uses following two step:
(1) by Mn (NO3)2It is dispersed in water for the silicon powder of 20.0nm by sodium tripolyphosphate with median particle diameter, stirs 1h,
By spray pyrolysis, by the product of acquisition, lotion, drying obtains presoma；
(2) presoma is in batch-type furnace with the heating rate of 5 DEG C/min, and under nitrogen atmosphere, 700 DEG C keep the temperature 4 hours, preparation
Obtain the composite material with porous structure；In the composite material, the molar percentage that silicon powder accounts for composite material is 25%, manganese
The molar percentage that oxide accounts for composite material is 75%.
Embodiment 2
The preparation method of the composite material of porous structure uses following two step:
(1) by silicon nanowires that cobalt acetate and median particle diameter are 100.0nm by lauryl sodium sulfate be scattered in from
In sub- water, 3h is stirred, spray drying obtains presoma；
(2) by presoma in pushed bat kiln, with the heating rate of 10 DEG C/min, under nitrogen atmosphere, 800 DEG C keep the temperature 6 hours,
The composite material with porous structure is prepared；In the composite material, the molar percentage that silicon nanowires accounts for composite material is
10%, the molar percentage that the oxide of cobalt accounts for composite material is 90%.
Embodiment 3
The preparation method of the composite material of porous structure uses following two step:
(1) Ni (NO for being 1:1:1 by mass ratio3)2、Co(NO3)2And MnSO4And median particle diameter is an oxygen of 50.0nm
SiClx disperses in aqueous solution, to add ammonium hydrogen carbonate, stirs 2h, and by being filtered, washed, drying obtains presoma；
(2) in rotary furnace, presoma will be obtained, with the heating rate of 15 DEG C/min, is protected under 900 DEG C, Krypton atmosphere
Temperature 2 hours, is prepared the composite material with porous structure；In the composite material, silicon monoxide accounts for mole of composite material
Percentage is 30%, and the molar percentage that nickel, cobalt and Mn oxide account for composite material altogether is 70%.
Embodiment 4
The preparation method of the composite material of porous structure uses following two step:
(1) by MnSO4The unformed silicon for being 20.0nm with median particle diameter, is dispersed in water by sodium tripolyphosphate, is stirred
Sodium carbonate is added in 1h, stirs 6 hours, washs, and filtering, drying obtains presoma；
(2) composite precursor will be obtained, in a vacuum furnace the heating rate of 1 DEG C/min, under nitrogen atmosphere, 500 DEG C of calcinings
48 hours, the composite material with porous structure is prepared；In the composite material, unformed silicon accounts for moles the hundred of composite material
Divide than being 40%, the molar percentage that the oxide of manganese accounts for composite material is 60%.
Embodiment 5
The preparation method of the composite material of porous structure uses following two step:
(1) Mn (NO for being 2:1 by mass ratio3)2And NiSO4And median particle diameter is the silicon nanowires and an oxygen of 250.0nm
SiClx is scattered in deionized water by cetyl trimethylammonium bromide, stirs 2.5h, and urea is added, at 60 DEG C, stirring 4
Hour, it washs, filtering obtains presoma；
(2) presoma will be obtained, in a nitrogen atmosphere, with the heating rate of 20 DEG C/min, will be forged for 1000 DEG C in tube furnace
It burns 1 hour, the composite material with porous structure is prepared；In the composite material, silicon nanowires and silicon monoxide account for again altogether
The molar percentage of condensation material is 70%, and the molar percentage that the oxide of manganese and nickel accounts for composite material altogether is 30%.
Embodiment 6
The preparation method of the composite material of porous structure uses following two step:
(1) by Cu (NiO3)2It is scattered in for the silicon monoxide of 100.0nm by lauryl sodium sulfate with median particle diameter
In ionized water, 3h is stirred, spray drying obtains presoma；
(2) by presoma in pushed bat kiln, with the heating rate of 10 DEG C/min, under nitrogen atmosphere, 800 DEG C keep the temperature 6 hours,
The composite material with porous structure is prepared；In the composite material, the molar percentage that silicon monoxide accounts for composite material is
50%, the molar percentage that the oxide of copper accounts for composite material is 50%.
Comparative example 1
Material proportion design and calcination condition and process are identical with embodiment 1, and difference is only that following steps.
(1) MnO and the median particle diameter silicon powder for being 20.0nm are dispersed in water by sodium tripolyphosphate, stir 1h, volatilization
Fall moisture content, obtains composite material；In the composite material, the molar percentage that silicon powder accounts for composite material is that 40%, 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, and difference is only that following steps.
(1) NiCO for being 1:1:1 by mass ratio3、CoCO3And MnCO3And the silicon monoxide that median particle diameter is 50.0nm is mixed
It closes uniform；In rotary furnace, with the heating rate of 15 DEG C/min, 2 hours are kept the temperature under 900 DEG C, Krypton atmosphere, is prepared multiple
Condensation material；In the composite material, the molar percentage that silicon monoxide accounts for composite material is 30%, and nickel, cobalt and Mn oxide account for altogether
The molar percentage of composite material is 70%.
Chemical property evaluation: the silicon based composite material of above-mentioned preparation is subjected to chemical property evaluation.Battery production, electricity
Chemical property test is as follows: the mass ratio of porous anode material, acetylene black and PVDF (Kynoar) is 80:10:10,
Porous anode material and acetylene black are uniformly mixed, PVDF (Kynoar) is then added, and (PVDF is prepared
The PVDF/NMP solution of 0.02g/mL, NMP are N-Methyl pyrrolidone) solution, be coated in copper foil on, in a vacuum drying oven in
120 DEG C are dried in vacuo 24 hours, take the disk that diameter is 19 centimetres as working electrode, lithium metal is to electrode, and electrolyte is
LiPF6/EC-DMC-EMC (volume ratio 1:1:1) is assembled into two electrode simulated batteries being full of in Ar glove box.Charging/discharging voltage
Range 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.
1 electrochemical property test result of table
Test result shows: using method of the invention, it is ensured that each component is uniformly dispersed under liquid phase, after heat treatment,
Formed porous structure, effectively inhibit generate stress caused by material structure destroy, thus improve material cyclical stability and
Capacity plays and first charge discharge efficiency.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (36)
1. a kind of composite material with porous structure, which is characterized in that with the transition metal oxide M of porous structurexOyFor bone
Frame is filled with nano-silicon in hole；
The composite material with porous structure is by using coprecipitation or spray drying process, with transition metal oxide
MxOyIt is prepared with silica-base material for raw material；
The preparation method of the composite material with porous structure, comprises the following steps that
(1) it disperses transition metal salt and nano-silicon in solvent, stir and is packed into reactor；
(2) it is co-precipitated or is spray-dried in the reactor to obtain transition metal carbonate presoma；
(3) the transition metal carbonate presoma is calcined at 400-1000 DEG C, is prepared with the compound of porous structure
Material.
2. composite material according to claim 1, which is characterized in that the transition metal oxide MxOy, x value range
Be 0 < y≤4, M Ni for 0 < x≤3, y value range, in Co, Mn, Ti, Cu any one or at least two mixture.
3. composite material according to claim 2, which is characterized in that the transition metal oxide MxOyFor NiO, CoO,
Co2O3、MnO、Mn2O3、Mn3O4、TiO2、Ti2O3、Cu2O, any one in CuO or at least two mixture.
4. composite material according to claim 3, which is characterized in that the transition metal oxide be NiO, CoO, CuO,
MnO、Mn2O3In any one or at least two mixture.
5. composite material according to claim 1 or 2, which is characterized in that the median particle diameter in the hole is 1.0-45.0 μm.
6. composite material according to claim 5, which is characterized in that the median particle diameter in the hole is 5.0-25.0 μm.
7. composite material according to claim 1, which is characterized in that the transition metal oxide MxOyIt accounts for described compound
The molar percentage of total amount of material is 30-99%, and the molar percentage that the nano-silicon accounts for the composite material total amount is 1-
70%.
8. composite material according to claim 7, which is characterized in that the transition metal oxide MxOyIt accounts for described compound
The molar percentage of total amount of material is 50-80%, and the molar percentage that the nano-silicon accounts for the composite material total amount is 20-
50%.
9. composite material according to claim 1, which is characterized in that the nano-silicon is crystalline silicon, amorphous silicon, oxidation
In silicon, silicon monoxide any one or at least two mixture.
10. composite material according to claim 9, which is characterized in that the nano-silicon is crystalline silicon, silica, an oxygen
In SiClx any one or at least two mixture.
11. composite material according to claim 1, which is characterized in that the median particle diameter of the nano-silicon is 20.0-
300.0nm。
12. composite material according to claim 11, which is characterized in that the median particle diameter of the nano-silicon is 25.0-
250.0nm。
13. composite material according to claim 12, which is characterized in that the median particle diameter of the nano-silicon is 30.0-
200.0nm。
14. a kind of method for preparing the composite material with porous structure, which is characterized in that comprise the following steps that
(1) it disperses transition metal salt and nano-silicon in solvent, stir and is packed into reactor；
(2) it is co-precipitated or is spray-dried in the reactor to obtain transition metal carbonate presoma；
(3) the transition metal carbonate presoma is calcined at 400-1000 DEG C, is prepared with the compound of porous structure
Material；
The composite material with porous structure is with the transition metal oxide M of porous structurexOyFor skeleton, filled out in hole
Filled with nano-silicon.
15. according to the method for claim 14, which is characterized in that the transition metal salt be transition metal nitrate,
In sulfate, chlorate any one or at least two mixture.
16. according to the method for claim 15, which is characterized in that the transition metal salt is 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)2In any one or at least two mixture.
17. according to the method for claim 14, which is characterized in that the transition metal ions contained in the transition metal salt
For Ni2+、Ni3+、Co2+、Co3+、Mn2+、Mn3+、Ti2+、Ti3+、Cu2+In any one or at least two mixture.
18. according to the method for claim 14, which is characterized in that the nano-silicon is crystalline silicon, amorphous silicon, oxidation
In silicon, silicon monoxide any one or at least two mixture.
19. according to the method for claim 18, which is characterized in that the nano-silicon is crystalline silicon, silica, silicon monoxide
In any one or at least two mixture.
20. according to the method for claim 14, which is characterized in that the median particle diameter of the nano-silicon is 20.0-
300.0nm。
21. according to the method for claim 20, which is characterized in that the median particle diameter of the nano-silicon is 25.0-
250.0nm。
22. according to the method for claim 21, which is characterized in that the median particle diameter of the nano-silicon is 30.0-
200.0nm。
23. according to the method for claim 14, which is characterized in that dispersing agent, the dispersion are used in step (1) dispersion
Agent is sodium tripolyphosphate, calgon, sodium pyrophosphate, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, fibre
Tie up plain derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, cetyl trimethylammonium bromide, polyethylene glycol pair
Isooctyl phenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid,
In polyetherimide any one or at least two mixture.
24. according to the method for claim 14, which is characterized in that step (1) solvent be water or organic solvent, it is described
Organic solvent be alcohol, ketone, in ether any one or at least two mixture.
25. according to the method for claim 14, which is characterized in that step (1) reactor be vacuum drying oven, batch-type furnace,
Rotary furnace, roller kilns, pushed bat kiln, any one in tube furnace.
26. according to the method for claim 14, which is characterized in that precipitating reagent is used in step (2) co-precipitation, described heavy
Shallow lake agent is carbonate and/or bicarbonate.
27. according to the method for claim 26, which is characterized in that step (2) precipitating reagent is ammonium carbonate and/or carbonic acid
Hydrogen ammonium.
28. according to the method for claim 14, which is characterized in that step (3) calcining carries out under protective atmosphere,
The protective atmosphere be nitrogen, helium, neon, argon gas, Krypton, in xenon any one or at least two mixture.
29. according to the method for claim 14, which is characterized in that the temperature of step (3) described calcining is 500-800 DEG C.
30. according to the method for claim 29, which is characterized in that the temperature of step (3) described calcining is 600-750 DEG C.
31. according to the method for claim 14, which is characterized in that the heating rate of step (3) described calcining is 1.0-
20.0℃/min。
32. according to the method for claim 31, which is characterized in that the heating rate of step (3) described calcining is 5.0-
15.0℃/min。
33. according to the method for claim 14, which is characterized in that the time of step (3) described calcining is 4-48h.
34. according to the method for claim 33, which is characterized in that the time of step (3) described calcining is 5-30h.
35. according to the method for claim 14, which is characterized in that the method includes the steps as follows:
(1) it disperses transition metal salt and nano-silicon in water or organic solvent by dispersing agent, is packed into reaction after stirring 1-4h
Device；
(2) carbonate and/or bicarbonate are added in the reactor, stirring obtains transition metal carbonate forerunner through co-precipitation
Body；
(3) the transition metal carbonate presoma calcines 4-48h under 400-1000 DEG C, protective atmosphere, and tool is prepared
There is the composite material of porous structure.
36. a kind of lithium ion battery, which is characterized in that using compound with porous structure as described in one of claim 1-13
Material is used as lithium ion battery negative material.
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| CN108134057A (en) * | 2017-12-05 | 2018-06-08 | 西北工业大学 | A kind of preparation method of high-tap density MnO/C negative materials |
| CN108574090A (en) * | 2018-03-13 | 2018-09-25 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN110289400B (en) * | 2019-05-27 | 2021-04-06 | 四川创能新能源材料有限公司 | A kind of dispersion 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 |
| CN114242960A (en) * | 2021-10-28 | 2022-03-25 | 广东邦普循环科技有限公司 | Hollow spherical particle anode material with opening and preparation method and application thereof |
| CN114388771A (en) * | 2022-03-07 | 2022-04-22 | 湖北亿纬动力有限公司 | Silicon-based composite negative electrode material, negative electrode sheet, preparation method thereof, and lithium ion battery |
| 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 |
| CN117486215B (en) * | 2023-10-30 | 2025-01-17 | 陕西科技大学 | Silicon-carbon negative electrode material modified by magnetic transition metal oxide and preparation method thereof |
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