CN110289414A - A kind of lithium ion battery negative material and preparation method thereof - Google Patents
A kind of lithium ion battery negative material and preparation method thereof Download PDFInfo
- Publication number
- CN110289414A CN110289414A CN201910599454.8A CN201910599454A CN110289414A CN 110289414 A CN110289414 A CN 110289414A CN 201910599454 A CN201910599454 A CN 201910599454A CN 110289414 A CN110289414 A CN 110289414A
- Authority
- CN
- China
- Prior art keywords
- bismuth
- lithium
- ion battery
- lithium titanate
- battery negative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 68
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 58
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 29
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 5
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 31
- 229910052593 corundum Inorganic materials 0.000 claims description 22
- 239000010431 corundum Substances 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000000428 dust Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- 239000011268 mixed slurry Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- QAKMMQFWZJTWCW-UHFFFAOYSA-N bismuth titanium Chemical compound [Ti].[Bi] QAKMMQFWZJTWCW-UHFFFAOYSA-N 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical group O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910010416 TiO(OH)2 Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910012330 Li3Bi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- H01M4/48—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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of lithium ion battery negative materials and preparation method thereof, are related to battery technology field.The lithium ion battery negative material uses bismuth doped titanic acid lithium material, and the method combined by high-energy ball milling with microwave process for synthesizing, and is rapidly cooled technique and is prepared.Bismuth doped lithium titanate material particle size obtained is small and is evenly distributed.And synthesis technology is easy, and easily operated, can be effectively reduced production energy consumption.Meanwhile the advantages of this method combination lithium titanate and BiOCl, bismuth doped titanic acid lithium material is prepared, on the basis of not destroying lithium titanate original crystal structure, material structure stability is not only ensure that, also effectively increases the specific capacity of lithium titanate material.So that lithium ion battery measured material specific capacity under 0.1C multiplying power electric current is 181.4mAh/g, capacity retention ratio is 96.5% after circulation 100 times.
Description
Technical field
The present invention relates to battery technology fields, in particular to lithium ion battery negative material and preparation method thereof.
Background technique
In current commercialized lithium ion battery, the carbon materials of form of graphite are the negative electrode materials being most widely used.
The electro-chemical activity of graphite is from Li+Insertion and deintercalation of the ion between its layer structure.However, in long-term charge and discharge cycles
Under, the crystal structure of graphite can collapse, and affect Li+The invertibity of insertion and the deintercalation of ion, to reduce battery
Service life.Also, due to lower (the < 0.1V vs Li/Li of carbon material electrode potential+), it is poor with electrolyte matching,
It is easy that Li dendrite is precipitated in charge and discharge process, further results in internal short-circuit of battery, thus there is biggish security risk.Cause
This, searching stable structure, long-life, high safety, the lithium ion battery negative material of high capacity are imperative.
Lithium titanate (the Li of spinel-type4Ti5O12) it is a kind of " zero strain " material, Li+Insertion and deintercalation only have to lattice
Slight contraction, caused phase transformation only cause the variation of volume small (0.2%), have good structural stability, thus
Possess superior cycle performance.Its discharge platform is 1.5V vsLi/Li+, discharge capacity reaches 175mAh/g, and under high potential
It is not easy that Li dendrite is precipitated, thus there is good safety, be considered as ideal negative electrode material.But due to its electrode potential
It is higher, cause operating voltage low, energy density reduces, to leverage the cruising ability of battery, significantly limits it
Scale application.Thus, the research focus being optimized to for researcher is modified to lithium titanate anode material.
In research so far, the ion to metatitanic acid lithium doping includes Fe3+、Ga3+、Mg2+、Al3+、Ni3+、Cr3+、Mo4+、
Mn3+、Co3+、V5+、La3+、Zr4+、V4+、F-And Br-Deng.The preparation method of lithium titanate material mainly has high temperature solid-state method, molten at present
Sol-gel and hydro-thermal method etc., traditional synthesis technology are bad to the material particle size control effect being synthesized, size
Unevenness causes the internal resistance of cell to increase, and influences the performance of battery performance.That there are specific capacities is low for lithium titanate material in the prior art, system
The defects of standby complex process and uneven particle diameter distribution.
There is researcher's discovery, BiOCl material can be used as the anode material in lithium ion battery, and theoretical specific capacity is up to
769mAh/g.Shown in the electrode reaction equation such as formula (1) of BiOCl and formula (2).However, BiOX (X is halogen) material exists
In charge and discharge process, volume expansion is serious, largely effects on the cycle life of battery, and is easy to cause safety problem, therefore
Its application receives huge limitation.
Formula (1): BiOCl+3Li++3e-→Li3OCl+Bi；
Formula (2): Bi+3Li++3e-→Li3Bi；
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of lithium ion battery negative material, and this method is simple and convenient, can have
Effect ground reduces production energy consumption.Meanwhile the advantages of this method combination lithium titanate and BiOCl, bismuth doped titanic acid lithium material is prepared,
It does not destroy on the basis of the original crystal structure of lithium titanate, not only ensure that material structure stability, also effectively increase lithium titanate
The specific capacity of material.So that lithium ion battery measured material specific capacity under 0.1C multiplying power electric current is 181.4mAh/g, circulation
Capacity retention ratio is 96.5% after 100 times.
Another object of the present invention is to provide a kind of lithium ion battery negative materials, are prepared by the above method
It arrives, the specific capacity of the lithium ion battery negative material is high, and particle diameter distribution is uniform, and performance is good.
The present invention is implemented as follows:
In a first aspect, the embodiment of the present invention provides a kind of preparation method of lithium ion battery negative material, comprising:
Titanium source, lithium source and bismuth source are dissolved in quantitative deionized water, and high-energy ball milling obtains mixing bismuth after mixing
Lithium titanate slurry；
Bismuth lithium titanate slurry will be mixed, granulation is dried, and obtained particle size dispersion and uniformly mix the mixing of bismuth lithium titanate precursor
Grain；
It will mix after bismuth lithium titanate precursor hybrid particles pass sequentially through and be put into corundum crucible, handled in microwave reactor
It obtains mixing bismuth lithium titanate powdery.
Specifically, this method synthesis technology is easy, and easily operated, can reduce production energy consumption.Meanwhile by by high energy
The method that ball milling is combined with microwave process for synthesizing, and it is rapidly cooled technique, obtained bismuth doped lithium titanate material particle size
It is small and be evenly distributed, the technical problem of lithium titanate material particle diameter distribution unevenness in the prior art can be efficiently solved.
In alternative embodiments, it is dissolved in quantitative deionized water by titanium source, lithium source and bismuth source, and high energy ball
Mill obtains mixing in bismuth lithium titanate slurry stage after mixing:
Ball milling uses high energy ball mill, the revolving speed 200r/min-1500r/min of ball mill, Ball-milling Time 1h-12h.And
In an embodiment of the present invention, the molar ratio of titanium source, lithium source and bismuth source is nTi:nLi:nBi=(8-13): (9-15): (0.05-
5), and titanium source, lithium source and bismuth source be dissolved in mixed slurry after quantitative deionized water it is solid containing control in 15%-60%.By titanium
Source, lithium source and the control of bismuth source are in the amount ranges, it is ensured that the quality for the lithium titanate material being finally prepared.Certainly,
In other embodiments of the invention, titanium source, lithium source and the specific dosage in bismuth source can also be selected according to demand, this hair
Bright embodiment is without limitation.
In alternative embodiments, titanium source is TiO2、TiO(OH)2One of or it is a variety of；Lithium source is Li2CO3、
LiNO3, one of LiOH or a variety of；Bismuth source is Bi2O3, one of BiOCl or a variety of.
Simultaneously, it should be noted that in the present embodiment, bismuth lithium titanate slurry will be mixed, granulation is dried, obtain partial size
In finely dispersed the step of mixing bismuth lithium titanate precursor hybrid particles, drying-granulating is using peristaltic pump the mixing after ball milling
Slurry is transferred to progress in the spray dryer for setting temperature and pressure.
In alternative embodiments, will mix bismuth lithium titanate precursor hybrid particles pass sequentially through be put into corundum crucible,
It obtains mixing in bismuth lithium titanate powdery step after being handled in microwave reactor, bismuth lithium titanate precursor hybrid particles will be mixed and be put into
Processing is carried out in corundum crucible to specifically include:
Bismuth lithium titanate precursor hybrid particles will be mixed to be transferred in corundum crucible and close the lid；
Corundum crucible is placed in the reaction vessel equipped with carbon dust, is enclosed in carbon dust around corundum crucible, and make corundum
The lid surface of crucible dissipates deposited carbon dust.
In alternative embodiments, will mix bismuth lithium titanate precursor hybrid particles pass sequentially through be put into corundum crucible,
It obtains mixing in bismuth lithium titanate powdery step after being handled in microwave reactor, bismuth lithium titanate precursor hybrid particles will be mixed and be put into
Processing is carried out in microwave reactor to specifically include:
Reaction vessel is transferred in microwave reactor, and carries out heating synthesis under an inert atmosphere；
After to be heated, reaction vessel is taken out, and obtain mixing bismuth lithium titanate powdery after carrying out fast cooling.
In alternative embodiments, it is transferred in microwave reactor by reaction vessel, and carries out under an inert atmosphere
It heats in synthesis step:
The inert gas being passed through is N2, He, Ar it is one or more, by being passed through for inert gas, can prevent from being used as
The carbon dust high-temperature oxydation of second heating medium.
In alternative embodiments, it is transferred in microwave reactor by reaction vessel, and carries out under an inert atmosphere
It heats in synthesis step:
The heating temperature of microwave reactor is 300 DEG C -600 DEG C, heating time 15min-120min.Certainly, in this hair
In bright other embodiments, heating temperature can also be adjusted according to demand, and the embodiment of the present invention is without limitation.
In alternative embodiments, after to be heated, reaction vessel is taken out, and mixed after carrying out fast cooling
In bismuth lithium titanate powdery step:
Fast cooling step is to cool down rapidly in low temperature bath, and low temperature bath is one kind or more of ice bath, water-bath, ice-water bath
Kind.Can inhibit particle by way of fast cooling to be further up to, thus obtain it is uniformly tiny mix bismuth lithium titanate powdery,
And then the advantages of combining lithium titanate and BiOCl, bismuth doped titanic acid lithium material is prepared, the original crystal structure of lithium titanate is not being destroyed
On the basis of, while ensure that material structure stability, the effective specific capacity for increasing lithium titanate material.
In alternative embodiments, further includes: the bismuth lithium titanate powdery of mixing after will be cooled to room temperature successively carries out dry method
Ball milling and sieving, and ball milling is carried out using ball mill, the revolving speed of ball mill is 200r/min-1500r/min, and Ball-milling Time is
1h-12h.It carries out being screened to 500 mesh after ball milling and target product can be obtained.
Second aspect, the embodiment of the present invention provide a kind of lithium ion battery negative material, and lithium ion battery negative material is logical
The preparation method for crossing the lithium ion battery negative material of any one of aforementioned embodiments is prepared.
The invention has the following advantages:
The lithium ion battery negative material uses bismuth doped titanic acid lithium material, and passes through high-energy ball milling and microwave process for synthesizing phase
In conjunction with method, and be rapidly cooled technique and be prepared.Bismuth doped lithium titanate material particle size obtained is small and is evenly distributed.
And synthesis technology is easy, and easily operated, can be effectively reduced production energy consumption.Meanwhile this method combination lithium titanate and BiOCl
The advantages of, bismuth doped titanic acid lithium material is prepared, on the basis of not destroying lithium titanate original crystal structure, not only ensure that material
Expect structural stability, also effectively increases the specific capacity of lithium titanate material.So that lithium ion battery institute under 0.1C multiplying power electric current
Measuring material specific capacity is 181.4mAh/g, and capacity retention ratio is 96.5% after circulation 100 times.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the SEM figure for the product that the embodiment of the present invention 1 is prepared；
Fig. 2 is the cycle life figure of the battery for the product preparation that the embodiment of the present invention 1 is prepared；
Fig. 3 is the charging and discharging curve figure of the battery of the product preparation arrived prepared by the embodiment of the present invention 1.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of lithium ion battery negative material is present embodiments provided, is prepared by the following method to obtain:
S1: weighing molar ratio respectively is nTi:nLi:nBiTitanium source, lithium source and the bismuth source of=8.1:10:1, and be added go from
Sub- water is adjusted to the solid containing being 40% of mixed slurry.Mixed slurry is passed through ball mill and carries out ball milling, drum's speed of rotation is set as
800r/min, Ball-milling Time 2.5h.
S2: the mixed slurry after ball milling is transferred in the spray dryer for setting temperature and pressure using peristaltic pump
(feeding temperature is 220 DEG C, and drop temperature is 90 DEG C, and pressure is 0.3MPa in drying machine), is dried granulation, obtains mixing bismuth titanium
Sour lithium presoma hybrid particles.
S3: being transferred to obtained bismuth lithium titanate precursor hybrid particles of mixing in corundum crucible and close the lid, then by corundum
Crucible is placed in the reaction vessel equipped with carbon dust, is enclosed in carbon dust around corundum crucible, and lid surface dissipates deposited carbon dust.
S4: reaction vessel is transferred in microwave reactor, is passed through 0.5MPa N2It is discharged after pressure maintaining 1min, repeats the step
To replace the air in microwave reactor, it is finally passed through 0.5MPa N rapid 3 times2As protection gas.Adding for microwave reactor, is set
Hot temperature is 480 DEG C, heating time 60min.
S5: it after heating, takes out beautiful crucible and is placed in ice-water bath, obtain mixing bismuth lithium titanate powder after being cooled to room temperature
Body.
S6: resulting bismuth doped titanic acid powder for lithium is transferred to ball mill and carries out dry ball milling, powder is slightly ground
Then mill crosses 500 meshes, obtains target product.
Experimental example 1
The product that embodiment 1 is prepared, using field emission scanning electron microscope (FE-SEM, Sirion-200, Philips)
It observes product morphology (Fig. 1), while being tested for the property using following test method.
The negative electrode material being prepared (mixing bismuth lithium titanate material) and conductive carbon black and PVDF is mixed with 9:0.5:0.5 ratio
Slurry is made in conjunction, is homogeneously applied on copper foil, and pole piece is made and makees anode, is lithium piece to electrode, is assembled into 2032 type button electricity
Pond.The button cell is under the current density of 0.1C (0.1C=18.1mA/g), in the voltage range of 1.0V-2.5V, test electricity
The charge/discharge capacity (Fig. 2) in pond.Meanwhile battery recycles 100 times (Fig. 3) under conditions of 0.1C, 1.0V-2.5V charge and discharge.
Embodiment 2
A kind of lithium ion battery negative material is present embodiments provided, is prepared by the following method to obtain:
S1: weighing molar ratio respectively is nTi:nLi:nBiTitanium source, lithium source and the bismuth source of=9.6:12:2.4, and be added and go
Ionized water is adjusted to the solid containing being 20% of mixed slurry.Mixed slurry is passed through ball mill and carries out ball milling, drum's speed of rotation setting
For 1200r/min, Ball-milling Time 5h.
S2: the mixed slurry after ball milling is transferred in the spray dryer for setting temperature and pressure using peristaltic pump
(feeding temperature is 220 DEG C, and drop temperature is 90 DEG C, and pressure is 0.3MPa in drying machine), is dried granulation, obtains mixing bismuth titanium
Sour lithium presoma hybrid particles.
S3: being transferred to obtained bismuth lithium titanate precursor hybrid particles of mixing in corundum crucible and close the lid, then by corundum
Crucible is placed in the reaction vessel equipped with carbon dust, is enclosed in carbon dust around corundum crucible, and lid surface dissipates deposited carbon dust.
S4: reaction vessel is transferred in microwave reactor, is passed through 0.5MPa N2It is discharged after pressure maintaining 1min, repeats the step
To replace the air in microwave reactor, it is finally passed through 0.5MPaN rapid 3 times2As protection gas.The heating of microwave reactor is set
Temperature is 600 DEG C, heating time 30min.
S5: it after heating, takes out beautiful crucible and is placed in ice-water bath, obtain mixing bismuth lithium titanate powder after being cooled to room temperature
Body.
S6: resulting bismuth doped titanic acid powder for lithium is transferred to ball mill and carries out dry ball milling, powder is slightly ground
Then mill crosses 500 meshes, obtains target product.
By embodiment 1 and the test chart of experimental example 1 and Fig. 1 to Fig. 3 it is found that the embodiment of the present invention prepares bismuth mixes
Miscellaneous lithium titanate material not only can guarantee material structure stability, may be used also on the basis of not destroying lithium titanate original crystal structure
Effectively to increase the specific capacity of lithium titanate material.Battery measured material specific capacity under 0.1C multiplying power electric current is
181.4mAh/g, capacity retention ratio is 96.5% after recycling 100 times.
In conclusion the preparation method for the lithium ion battery negative material that the embodiment of the present invention provides is simple and convenient, it can
It is effectively reduced production energy consumption.Meanwhile the advantages of this method combination lithium titanate and BiOCl, bismuth doped titanic acid lithium material is prepared,
On the basis of not destroying lithium titanate original crystal structure, it not only ensure that material structure stability, also effectively increase metatitanic acid
The specific capacity of lithium material.So that lithium ion battery measured material specific capacity under 0.1C multiplying power electric current is 181.4mAh/g, follow
Capacity retention ratio is 96.5% after ring 100 times.The lithium ion battery negative material that the embodiment of the present invention provides passes through above-mentioned side
Method is prepared, and the specific capacity of the lithium ion battery negative material is high, and particle diameter distribution is uniform, and performance is good.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium ion battery negative material characterized by comprising
Titanium source, lithium source and bismuth source are dissolved in quantitative deionized water, and high-energy ball milling obtains mixing bismuth metatitanic acid after mixing
Lithium slurry；
Granulation is dried in the bismuth lithium titanate slurry of mixing, particle size dispersion is obtained and uniformly mixes the mixing of bismuth lithium titanate precursor
Grain；
It is mixed described after bismuth lithium titanate precursor hybrid particles pass sequentially through and be put into corundum crucible, handled in microwave reactor
It obtains mixing bismuth lithium titanate powdery.
2. the preparation method of lithium ion battery negative material according to claim 1, which is characterized in that described by titanium
Source, lithium source and bismuth source are dissolved in quantitative deionized water, and high-energy ball milling obtains mixing bismuth lithium titanate slurry step after mixing
In rapid:
The molar ratio of the titanium source, the lithium source and the bismuth source is nTi:nLi:nBi=(8-13): (9-15): (0.05-5),
And the titanium source, the lithium source and the bismuth source be dissolved in mixed slurry after quantitative deionized water it is solid containing control in 15%-
60%.
3. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that:
The titanium source is TiO2、TiO(OH)2One of or it is a variety of；
The lithium source is Li2CO3、LiNO3, one of LiOH or a variety of；
The bismuth source is Bi2O3, one of BiOCl or a variety of.
4. the preparation method of lithium ion battery negative material according to claim 1, which is characterized in that it is described will be described
Mix bismuth lithium titanate precursor hybrid particles pass sequentially through be put into corundum crucible, handled in microwave reactor after obtain mixing bismuth titanium
In sour powder for lithium step, by it is described mix bismuth lithium titanate precursor hybrid particles be put into corundum crucible carry out processing specifically include:
The bismuth lithium titanate precursor hybrid particles of mixing are transferred in corundum crucible and close the lid；
The corundum crucible is placed in the reaction vessel equipped with carbon dust, is enclosed in carbon dust around the corundum crucible, and make
The lid surface of the corundum crucible dissipates deposited carbon dust.
5. the preparation method of lithium ion battery negative material according to claim 4, which is characterized in that it is described will be described
Mix bismuth lithium titanate precursor hybrid particles pass sequentially through be put into corundum crucible, handled in microwave reactor after obtain mixing bismuth titanium
In sour powder for lithium step, by it is described mix bismuth lithium titanate precursor hybrid particles and be put into carry out handling specific packet in microwave reactor
It includes:
The reaction vessel is transferred in the microwave reactor, and carries out heating synthesis under an inert atmosphere；
After to be heated, the reaction vessel is taken out, and obtain after fast cooling described mixing bismuth lithium titanate powdery.
6. the preparation method of lithium ion battery negative material according to claim 5, which is characterized in that it is described will be described
Reaction vessel is transferred in the microwave reactor, and is carried out in heating synthesis step under an inert atmosphere:
The inert gas being passed through is N2, He, Ar it is one or more.
7. the preparation method of lithium ion battery negative material according to claim 5, which is characterized in that it is described will be described
Reaction vessel is transferred in the microwave reactor, and is carried out in heating synthesis step under an inert atmosphere:
The heating temperature of the microwave reactor is 300 DEG C -600 DEG C, heating time 15min-120min.
8. the preparation method of lithium ion battery negative material according to claim 5, which is characterized in that described to be heated
After, the reaction vessel is taken out, and obtain described mix in bismuth lithium titanate powdery step after carrying out fast cooling:
The fast cooling step is to cool down rapidly in low temperature bath, and low temperature bath is one kind or more of ice bath, water-bath, ice-water bath
Kind.
9. the preparation method of lithium ion battery negative material according to claim 5, which is characterized in that further include:
The bismuth lithium titanate powdery of mixing after will be cooled to room temperature successively carries out dry ball milling and sieving, and ball milling uses ball mill
It carries out, the revolving speed of the ball mill is 200r/min-1500r/min, Ball-milling Time 1h-12h.
10. a kind of lithium ion battery negative material, which is characterized in that the lithium ion battery negative material passes through claim 1
Preparation method to lithium ion battery negative material described in any one of 9 is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910599454.8A CN110289414A (en) | 2019-07-04 | 2019-07-04 | A kind of lithium ion battery negative material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910599454.8A CN110289414A (en) | 2019-07-04 | 2019-07-04 | A kind of lithium ion battery negative material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110289414A true CN110289414A (en) | 2019-09-27 |
Family
ID=68021927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910599454.8A Pending CN110289414A (en) | 2019-07-04 | 2019-07-04 | A kind of lithium ion battery negative material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110289414A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333001A (en) * | 2008-07-18 | 2008-12-31 | 东莞市迈科科技有限公司 | Method for preparing lithium titanate by microwave method |
| CN101373829A (en) * | 2008-10-07 | 2009-02-25 | 深圳市贝特瑞新能源材料股份有限公司 | Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery |
| CN102074681A (en) * | 2010-12-03 | 2011-05-25 | 广东工业大学 | Method for preparing carbon nano tube doped lithium titanate composite electrode material |
| CN102376937A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院金属研究所 | Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof |
| CN102891302A (en) * | 2011-07-19 | 2013-01-23 | 西门子公司 | Lithium titanate active substance, preparation method of the lithium titanate active substance and rechargeable lithium battery |
| CN102931386A (en) * | 2012-10-11 | 2013-02-13 | 广东工业大学 | Method for preparing carbon nano tube doped lithium titanate composite electrode material |
| CN103066267A (en) * | 2012-12-07 | 2013-04-24 | 上海锦众信息科技有限公司 | Preparation method of lithium titanate-carbon composite material of lithium ion battery |
| US20130119306A1 (en) * | 2011-11-11 | 2013-05-16 | Min-Sang Song | Composite, method of manufacturing the composite, negative electrode active material including the composite, negative electrode including the negative electrode active material, and lithium secondary battery including the same |
| CN104081565A (en) * | 2011-11-18 | 2014-10-01 | 克拉里安特国际有限公司 | Doped lithium titanium spinel compound and electrode comprising same |
-
2019
- 2019-07-04 CN CN201910599454.8A patent/CN110289414A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333001A (en) * | 2008-07-18 | 2008-12-31 | 东莞市迈科科技有限公司 | Method for preparing lithium titanate by microwave method |
| CN101373829A (en) * | 2008-10-07 | 2009-02-25 | 深圳市贝特瑞新能源材料股份有限公司 | Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery |
| CN102376937A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院金属研究所 | Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof |
| CN102074681A (en) * | 2010-12-03 | 2011-05-25 | 广东工业大学 | Method for preparing carbon nano tube doped lithium titanate composite electrode material |
| CN102891302A (en) * | 2011-07-19 | 2013-01-23 | 西门子公司 | Lithium titanate active substance, preparation method of the lithium titanate active substance and rechargeable lithium battery |
| US20130119306A1 (en) * | 2011-11-11 | 2013-05-16 | Min-Sang Song | Composite, method of manufacturing the composite, negative electrode active material including the composite, negative electrode including the negative electrode active material, and lithium secondary battery including the same |
| CN104081565A (en) * | 2011-11-18 | 2014-10-01 | 克拉里安特国际有限公司 | Doped lithium titanium spinel compound and electrode comprising same |
| CN102931386A (en) * | 2012-10-11 | 2013-02-13 | 广东工业大学 | Method for preparing carbon nano tube doped lithium titanate composite electrode material |
| CN103066267A (en) * | 2012-12-07 | 2013-04-24 | 上海锦众信息科技有限公司 | Preparation method of lithium titanate-carbon composite material of lithium ion battery |
Non-Patent Citations (5)
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108847477B (en) | Nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof | |
| EP3460887B1 (en) | Cathode active material for all-solid-state lithium secondary battery | |
| US9437873B2 (en) | Spinel-type lithium manganese-based composite oxide | |
| CN112952049A (en) | Method for repairing surface structure of high-nickel anode material, high-nickel anode material obtained by method and lithium ion battery | |
| CN103794777B (en) | A kind of preparation method of surface coated nickel lithium manganate cathode material | |
| CN111261851B (en) | Ternary cathode material of lithium ion battery and preparation method thereof | |
| WO2022206910A1 (en) | Cobalt-free high-nickel positive electrode material, preparation method therefor and use thereof | |
| CN102694167A (en) | Modified lithium manganate positive pole material and preparation method thereof | |
| CN104953107A (en) | Preparation method of lithium titanate cathode material with high tap density | |
| CN105789581A (en) | Production method for high-capacity long-cycle lithium-rich type-622 ternary positive electrode material | |
| CN112054166B (en) | Core-shell structure electrochemical active material, preparation method and battery | |
| JP2016185903A (en) | Manufacturing method of lithium manganese composite oxide | |
| CN111924885B (en) | Lithium cobaltate positive electrode material and modification method thereof | |
| CN107204429A (en) | The preparation method and anode material for lithium-ion batteries and lithium ion battery of nickel-cobalt-manganese ternary material | |
| CN105789582A (en) | Lithium titanate/porous carbon composite material and preparation method of lithium titanate/porous carbon composite material | |
| CN106784820B (en) | Nano lithium titanate negative electrode material for lithium ion battery and preparation method and application thereof | |
| WO2023056767A1 (en) | Preparation method for high-rate lithium iron phosphate positive electrode material | |
| CN113745493A (en) | Preparation method of graphene modified high-nickel positive electrode material | |
| CN106207154A (en) | Method for preparing anode material, positive electrode and battery | |
| CN111003733A (en) | Method for preparing high-nickel ternary lithium battery anode material through microwave intelligent frequency conversion second-order sintering | |
| CN102157725B (en) | The method of microwave sintering synthesis nickel-cobalt-manganmultielement multielement lithium ion battery positive electrode material | |
| CN106099082A (en) | The surface cladding type nickel ion doped material of a kind of hydro-thermal method modification, lithium battery and preparation method thereof | |
| CN103794758B (en) | The preparation method of vapour deposition process coating-doping lithium manganate composite anode material | |
| CN105810901A (en) | Ti<3+>/Ti<4+> mixed-valence lithium titanate negative electrode material doped with iron element and preparation of negative electrode material | |
| CN110931792B (en) | Coated silicon-based material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190927 |