CN103378355B - Alkali metal secondary battery and the preparation method of negative electrode active material, negative material, negative pole and negative electrode active material - Google Patents
Alkali metal secondary battery and the preparation method of negative electrode active material, negative material, negative pole and negative electrode active material Download PDFInfo
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Abstract
The invention discloses a kind of alkali metal secondary battery and the preparation method of negative electrode active material, negative material, negative pole and negative electrode active material, the chemical formula of negative electrode active material is: [A
(x-y)b
y] [B
x/3ti
(1-x/3)] O
2-δ, wherein, A, B adopt K, Na and Li one wherein respectively; 0 < x≤1,0≤y < x, 0≤δ≤1.The negative electrode active material of alkali metal secondary battery of the present invention has homogeneous reaction, in sodium-ion battery between voltage range 0.5 ~ 1.2V, voltage range 0.7-1.5V in lithium ion battery, the phenomenon can effectively avoiding sodium metal to deposit on negative pole, also has higher capacity.
Description
Technical field
The present invention relates to the preparation method of a kind of negative material of the titanate for alkali metal secondary battery, negative material, negative pole and negative material, and adopt the alkali metal secondary battery of this negative material.
Background technology
Alkali metal secondary battery mainly comprises lithium rechargeable battery and sodium ion secondary battery etc.
Since the end of the eighties, Sony Inc. produced first lithium ion battery, with its high-energy-density, long circulation life, the features such as environmental pollution is little, miniaturized electronics is widely used, and starts in recent years to be applied to electric motor car and large-scale energy storage device.But along with the consumption day by day of lithium resource, people start to turn one's attention to the sodium of resource more horn of plenty, recently get more and more to the research of sodium-ion battery.
From current report, alkali metal secondary battery negative material mainly contains the graphitic carbon in alkali metal, material with carbon element, amorphous and non-porous carbon black, carbon alloy and metal oxide.Alkali metal all easily produces metallic dendrite as negative material and occurs the safety problems such as short circuit in charge and discharge cycles.Have much relations for the graphite in material with carbon element as negative pole and self degree of graphitization and self property, amorphous carbon and specific area degree very large.Alkali metal alloy is larger as negative electrode volume expansion, and cyclical stability is bad, moreover does not also find good alloy cycle performance and capacity very good so far.Metal oxide is also a lot of as the problem of alkali metal secondary battery negative material, and such as discharge and recharge polarization is large, and circulation is unstable, and coulombic efficiency is low.
Mainly practical cathode material lithium ion battery mainly concentrates on graphite material, for Li now
4ti
5o
12then there is the problems such as flatulence, and sodium-ion battery never has stable circulation, the negative material that coulombic efficiency is high.
Therefore, finding that a kind of capacity is high, coulombic efficiency is high, good cycle, low-cost negative material, is that alkali metal secondary battery is in energy storage and the practical key moving towards practicality.
Summary of the invention
The object of the present invention is to provide a kind of alkali metal secondary battery negative electrode active material with homogeneous reaction and preparation method thereof, current alkali metal secondary battery negative material current potential can be overcome lower and easily form the defect of alkali metal deposition.
Another object of the present invention is to provide the negative material, negative pole and the alkali metal secondary battery that adopt this negative material.
The invention provides a kind of alkali metal secondary battery negative electrode active material, the chemical formula of this negative electrode active material is: [A
(x-y)b
y] [B
x/3ti
(1-x/3)] O
2-δ, wherein, A, B adopt K, Na and Li one wherein respectively; 0 < x≤1,0≤y < x, 0≤δ≤1.
Preferably, A is Na, B is Li; 0.5≤x≤0.8,0≤y < x, 0≤δ≤0.1.
Present invention also offers the preparation method of described negative electrode active material, described preparation method can be selected from any one in solid phase method and sol-gel process.
Described sol-gel process comprises the steps:
1) take appropriate alkali-metal acetate and butyl titanate according to the stoichiometric proportion of negative electrode active material and be dissolved in absolute ethyl alcohol respectively, in whipping process, the ethanol solution of alkali metal acetic acid is slowly joined in the ethanol solution of butyl titanate, and add citric acid, form aqueous precursor gel;
2) gained aqueous precursor gel is placed in crucible in 250-500 DEG C of preliminary treatment two hours, then processes 8 ~ 20 hours at 750-1000 DEG C, grind and obtain described negative electrode active material.
Described solid phase method comprises the steps:
1) by alkali-metal carbonate, titanyl compound, mix according to the stoichiometric proportion of negative electrode active material, after grinding evenly precursor powder;
2) gained precursor powder is placed in crucible and processes 8 ~ 25 hours at 650 ~ 1000 DEG C, grind and obtain described negative electrode active material.
Preparation in accordance with the present invention, wherein, any one in following methods can be adopted one or more of the coated carbon-coating of described negative electrode active material, metal level, nitride layer, oxide skin(coating) and high polymer layer: (1) adds sucrose, glucose, organic polymer, ionic liquid or slaine in described precursor powder or gel, and at Ar or N
2heat treated under inert gas shielding; (2) in described negative electrode active material, sucrose, glucose, organic polymer, ionic liquid or slaine is added, and at Ar or N
2heat treated under Buchholz protection; (3) thermal vapor deposition method is adopted to carry out coated to described presoma or described negative electrode active material.
The invention provides a kind of alkali metal secondary battery negative material, described negative material can comprise conductive additive and binding agent, can also comprise negative electrode active material of the present invention or the obtained negative electrode active material according to preparation method of the present invention.
The invention provides a kind of alkali metal secondary battery negative pole, described negative pole can comprise negative material of the present invention and collector.
The invention provides a kind of alkali metal secondary battery, described alkali metal secondary battery can comprise positive pole and negative pole of the present invention, and is placed in the electrolyte between described positive pole and described negative pole.
During by described negative electrode active material for the preparation of alkali metal secondary battery negative material and negative pole, the general manufacture method of existing lithium ion battery or sodium-ion battery can be adopted.That is, using negative electrode active material of the present invention and the powder ground and mixed such as (as rare in carbon black, acetylene black, graphite powder, carbon nano-tube, graphite) as conductive additive, described conductive additive accounts for 0 ~ 30wt%.Then with general binder solution (PVDF (polyvinylidene fluoride), Sodiumalginate (sodium alginate), CMC (sodium carboxymethylcellulose), SBR (butadiene-styrene rubber) etc.), can be such as NMP (1-METHYLPYRROLIDONE) solution of PVDF (polyvinylidene fluoride), be mixed into uniform sizing material, be coated on (as Copper Foil, titanium foil, nickel screen, nickel foam etc.) on collector and prepare electrode slice, after coating, the thickness of gained film can be 2 ~ 500 μm.The electrode obtained sheet is cut into applicable shape, for subsequent use after drying at 100 ~ 150 DEG C in the environment being essentially vacuum.
Improvements in described alkali metal secondary battery are to use negative electrode active material provided by the invention, and other part and preparation method are conventionally known to one of skill in the art, repeat no more herein.Described alkali metal secondary battery can be water system, non-water or all solid state alkali metal secondary battery.
Sodium-ion battery in alkali metal secondary battery of the present invention have cost low, have extended cycle life, energy density high, the extensive energy storage device needed for solar energy, wind power generation can be widely used in, and the field such as intelligent grid peak regulation, distribution power station, back-up source, communication base station, be especially suitable as extensive energy storage device.
The negative electrode active material of alkali metal secondary battery of the present invention has homogeneous reaction, in sodium-ion battery between voltage range 0.5 ~ 1.2V, voltage range 0.7-1.5V in lithium ion battery, the phenomenon can effectively avoiding sodium metal to deposit on negative pole, also has higher capacity (first all discharge capacities are greater than 120mAh/g under C/10).
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 shows X-ray diffraction (XRD) collection of illustrative plates of the negative electrode active material of the embodiment of the present invention 1;
Fig. 2 shows ESEM (SEM) figure of the negative electrode active material of the embodiment of the present invention 1;
Fig. 3 shows first 5 weeks charging and discharging curves of the sodium-ion battery of the embodiment of the present invention 1;
Fig. 4 shows first 4 weeks charging and discharging curves of the lithium ion battery of the embodiment of the present invention 2;
Fig. 5 shows the non-carbon coated of the embodiment of the present invention 3 and the charging and discharging curve of carbon coated sodium-ion battery.
Fig. 6 shows the head week charging and discharging curve of the sodium-ion battery of the embodiment of the present invention 4;
Fig. 7 shows the head week charging and discharging curve of the lithium ion battery of the embodiment of the present invention 5.
Embodiment
Further illustrate the present invention below by specific embodiment, but should be understood to, these embodiments are only used for the use specifically described more in detail, and should not be construed as limiting the present invention in any form.
General description is carried out to the material used in the present invention's test and test method in this part.Although for realizing many materials that the object of the invention uses and method of operation is well known in the art, the present invention still describes in detail as far as possible at this.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and method of operation are well known in the art.
Embodiment 1
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts solid phase method to prepare negative electrode active material Na
0.66li
0.22ti
0.78o
2, concrete steps are: by nano-anatase TiO
2(grain diameter is 50 ~ 100nm), Li
2cO
3(analyzing pure) and Na
2cO
3stoichiometrically mix, mixed grinding half an hour in agate mortar, obtain presoma, to gained presoma at 20MPa compressing tablet, gained disk diameter is about 1.5cm, and forerunner's body piece is transferred to Al by thickness 0.4cm
2o
3in crucible, in Muffle furnace, process 20 hours at 1000 DEG C, gained white powder sheet is for subsequent use after grinding, is negative electrode active material Na of the present invention
0.66li
0.22ti
0.78o
2, its XRD collection of illustrative plates and SEM figure are shown in Fig. 1 and Fig. 2.As can be seen from Fig. 1 and Fig. 2, this negative electrode active material to be particle diameter be particle of 2 ~ 10 μm, and be Na
0.66li
0.22ti
0.78o
2pure phase.
Above-mentioned negative electrode active material is prepared into sodium-ion battery.Concrete steps are: by the negative electrode active material Na prepared
0.66li
0.22ti
0.78o
2powder mixes according to the weight ratio of 60: 30: 10 with acetylene black, binding agent PVDF, add appropriate nmp solution, in the environment of air drying, grinding forms slurry, then slurry is evenly coated on copper foil of affluxion body or aluminium foil, the pole piece of 8 × 8mm is cut into after drying, under vacuum in 100 DEG C of dryings 10 hours, be transferred to glove box immediately for subsequent use.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal sheet as to electrode, the NaClO of 1M
4/ PC (propylene carbonate) solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to test, discharging by voltage is 0V, and charging by voltage is 3.0V, and all tests are all carried out under C/10 current density.Test result is shown in Fig. 3, and wherein a1, a2, b1, b2 are respectively first week charging curve, first week discharge curve, the 5th week charging curve, the 5th week discharge curve.Found out by Fig. 3, its first all discharge capacity can reach 290mAh/g, and first all coulombic efficiencies are about 62%, and charge and discharge current potential is about 0.5 ~ 1.2V.
Embodiment 2
The present embodiment is for illustration of the application of negative electrode active material of the present invention in lithium ion battery.
The present embodiment adopts embodiment 1 solid phase method to prepare negative electrode active material Na
0.66li
0.22ti
0.78o
2.
Above-mentioned negative electrode active material is prepared into lithium ion battery.Concrete steps are: by the negative electrode active material Na prepared
0.66li
0.22ti
0.78o
2powder mixes according to the weight ratio of 60: 30: 10 with acetylene black, binding agent PVDF, add appropriate nmp solution, in the environment of air drying, grinding forms slurry, then slurry is evenly coated on copper foil of affluxion body, the pole piece of 8 × 8mm is cut into after drying, under vacuum in 100 DEG C of dryings 10 hours, be transferred to glove box immediately for subsequent use.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using metal lithium sheet as to electrode, the LiBF of 1M
6/ PC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to test, discharging by voltage is 0V, and charging by voltage is 3.0V, and all tests are all carried out under C/10 current density.Test result is shown in Fig. 4, and wherein c1, c2, d1, d2 are respectively first week charging curve, first week discharge curve, 4th week charging curve, 4th week discharge curve.Found out by Fig. 3, its first all discharge capacity can reach 440mAh/g, and first all coulombic efficiencies are about 75%, and charge and discharge current potential is about 0.8 ~ 1.5V.
Embodiment 3
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts sol-gel process to prepare negative electrode active material Na
0.66li
0.22ti
0.78o
2, and the coated process of carbon is carried out to it.Concrete steps are: by butyl titanate (Ti (C
4h
9o)
4), lithium acetate (CH
3cOOLi) sodium acetate ((CH
3cOONa) take in right amount according to stoichiometric proportion, and be dissolved in absolute ethyl alcohol respectively.The ethanol solution of lithium acetate is joined gradually in the ethanol solution of carbonic acid four butyl ester in whipping process, and add appropriate citric acid to suppress hydrolysis, form aqueous precursor gel gradually, gained aqueous precursor gel is transferred to Al
2o
3at 900 DEG C, process 20 hours in crucible, obtain white powder after grinding for subsequent use.By this white powder and ionic liquid [EMIm] [N (CN)
2] (1-ethyl-3-methylimidazoliumdicyanamide) mix, and carry out pyrolysis in 600 DEG C of heating 4h in an ar atmosphere, namely obtain the negative electrode active material Na that carbon is coated after cooling
0.66li
0.22ti
0.78o
2/ C, wherein the thickness of N doping carbon-coating is essentially 1 ~ 10nm.Also other feasible methods can be used herein by coated for described negative electrode active material carbon-coating, or covered with metal layer, nitride layer, oxide skin(coating) and high polymer layer etc.
Negative electrode active material coated for above-mentioned carbon is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1, and carry out C/10 electric discharge to battery, test result is shown in Fig. 5, wherein e1, e2 are respectively first week charging curve and first week discharge curve, f1 and f2 is the process of non-bag carbon.As seen from Figure 5, first all coulombic efficiencies, by 68% of non-bag carbon, have brought up to 80%.
Embodiment 4
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts solid phase method to prepare negative electrode active material Na
0.51li
0.17ti
0.83o
2, concrete steps are: by TiO
2, Li
2cO
3and Na
2cO
3according to stoichiometric proportion mixing, in agate jar, 900 revs/min of mixing 4 hours of dry grinding, obtain the precursor powder of white; By the tableting under pressure of gained powder at 20MPa, gained forerunner body piece is transferred to Al
2o
3in crucible, 1000 DEG C of heat treatment 15 hours in air atmosphere, it is for subsequent use that obtained sheet obtains powder after grinding, is negative electrode active material Na of the present invention
0.51li
0.17ti
0.83o
2.
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test voltage scope is 0.4V-2.5V, and test result is shown in Fig. 6.Fig. 6 is first week charging and discharging curve.As seen from Figure 6, its first all discharge capacity can reach 147mAh/g, and first all coulombic efficiencies are about 73.5%, and after circulating five weeks, capacity is 108mAh/g.
Embodiment 5
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the material synthesized by embodiment 4 to dress up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Voltage tester scope is 0.7-2.5V, and test result is shown in Fig. 7, and its first all discharge capacity can reach 223mAh/g, and first all coulombic efficiencies are about 69%, and after circulating five weeks, capacity is 153mAh/g.
Embodiment 6
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts solid phase method to prepare negative electrode active material Na
0.54li
0.18ti
0.82o
2, concrete steps are: by nano-anatase TiO
2(grain diameter is 50 ~ 100nm), Li
2cO
3(analyzing pure) and Na
2cO
3stoichiometrically mix, mixed grinding half an hour in agate mortar, obtain presoma, precursor powder is transferred to Al
2o
3in crucible, in Muffle furnace, process 20h at 1000 DEG C, gained white powder sheet is for subsequent use after grinding, is negative electrode active material Na of the present invention
0.54li
0.18ti
0.82o
2.
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test voltage scope is 0.4V-2.5V, the results are shown in following table 1.
Embodiment 7
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the material synthesized by embodiment 6 to dress up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test result is in table 1.
Embodiment 8
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts solid phase method to prepare negative electrode active material Na
0.6li
0.2ti
0.8o
2, concrete steps are: by nano-anatase TiO
2(grain diameter is 50 ~ 100nm), Li
2cO
3(analyzing pure) and Na
2cO
3stoichiometrically mix, mixed grinding half an hour in agate mortar, obtain presoma, precursor powder is transferred to Al
2o
3in crucible, in Muffle furnace, process 20 hours at 1000 DEG C, gained white powder sheet is for subsequent use after grinding, is negative electrode active material Na of the present invention
0.6li
0.2ti
0.8o
2.
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test voltage scope is 0.4V-2.5V, the results are shown in following table 1.
Embodiment 9
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the material synthesized by embodiment 8 to dress up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test result is in table 1.
Embodiment 10
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts solid phase method to prepare negative electrode active material Na
0.75li
0.25ti
0.75o
2, concrete steps are: by nano-anatase TiO
2(grain diameter is 50 ~ 100nm), Li
2cO
3(analyzing pure) and Na
2cO
3stoichiometrically mix, mixed grinding half an hour in agate mortar, obtain presoma, precursor powder is transferred to Al
2o
3in crucible, in Muffle furnace, process 20h at 1000 DEG C, gained white powder sheet is for subsequent use after grinding, is negative electrode active material Na of the present invention
0.75li
0.25ti
0.75o
2.
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test voltage scope is 0.4V-2.5V, the results are shown in following table 1.
Embodiment 11
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the material synthesized by embodiment 10 to dress up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test result is in table 1.
Embodiment 12
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts sol-gel process to prepare negative electrode active material Na
0.81li
0.27ti
0.73o
2, and the coated process of carbon is carried out to it.Concrete steps are: by butyl titanate (Ti (C
4h
9o)
4), lithium acetate (CH
3cOOLi) sodium acetate ((CH
3cOONa) take in right amount according to stoichiometric proportion, and be dissolved in absolute ethyl alcohol respectively.The ethanol solution of lithium acetate is joined gradually in the ethanol solution of carbonic acid four butyl ester in whipping process, and add appropriate citric acid to suppress hydrolysis, form aqueous precursor gel gradually, gained aqueous precursor gel is transferred to Al
2o
3at 900 DEG C, process 20 hours in crucible, obtain white powder after grinding for subsequent use.Be negative electrode active material Na of the present invention
0.81li
0.27ti
0.73o
2.
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test voltage scope is 0.5V-2.5V, the results are shown in following table 1.
Embodiment 13
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the material synthesized by embodiment 12 to dress up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test result is in table 1.
Embodiment 14
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts solid phase method to prepare negative electrode active material [Na
2/7li
1/7] [Li
1/7ti
2/7] O
2concrete steps are: by nano-anatase TiO
2(grain diameter is 50 ~ 100nm), Li
2cO
3(analyzing pure) and Na
2cO
3stoichiometrically mix, mixed grinding half an hour in agate mortar, obtain presoma, precursor powder is transferred to Al
2o
3in crucible, in Muffle furnace, process 15h at 1000 DEG C, gained white powder sheet is for subsequent use after grinding, is negative electrode active material [Na of the present invention
2/7li
1/7] [Li
1/7ti
2/7] O
2.
Above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test voltage scope is 0.7V-2.5V, the results are shown in following table 1.
Embodiment 15
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts solid phase method to prepare negative electrode active material Na
0.77li
0.31ti
0.73o
1.97concrete steps are: by nano-anatase TiO
2(grain diameter is 50 ~ 100nm), Li
2cO
3(analyzing pure) and Na
2cO
3stoichiometrically mix, mixed grinding half an hour in agate mortar, obtain presoma, precursor powder is transferred to Al
2o
3in crucible, in Muffle furnace, process 18 hours at 950 DEG C, gained white powder sheet is for subsequent use after grinding, is negative electrode active material Na of the present invention
0.77li
0.31ti
0.73o
1.97.
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test voltage scope is 0.3V-2.5V, the results are shown in following table 1.
Embodiment 16
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the material synthesized by embodiment 13 to dress up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test result is in table 1.
Embodiment 17
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts sol-gel process to prepare negative electrode active material Na
0.69li
0.23ti
0.77o
1.99.Concrete steps are: by butyl titanate (Ti (C
4h
9o)
4), lithium acetate (CH
3cOOLi) sodium acetate ((CH
3cOONa) take in right amount according to stoichiometric proportion, and be dissolved in absolute ethyl alcohol respectively.The ethanol solution of lithium acetate is joined gradually in the ethanol solution of carbonic acid four butyl ester in whipping process, and add appropriate citric acid to suppress hydrolysis, form aqueous precursor gel gradually, gained aqueous precursor gel is transferred to Al
2o
3at 850 DEG C, process 25 hours in crucible, obtain white powder after grinding for subsequent use.Be negative electrode active material Na of the present invention
0.69li
0.23ti
0.77o
1.99.
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test voltage scope is 0.5V-2.5V, the results are shown in following table 1.
Embodiment 18
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the material synthesized by embodiment 17 to dress up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test result is in table 1.
Embodiment 19
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the active material synthesized by embodiment 17, utilizes the Al of ald (ALD) 2nm
2o
3, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its method of testing is with embodiment 2.Test result is in table 1.
Embodiment 20
The present embodiment is for illustration of the preparation of negative electrode active material of the present invention and application thereof.
The present embodiment adopts the active material synthesized by embodiment 17; directly above-mentioned material and PAM (polyacrylamide) are mixed according to 6%: 94%; 750 degree of process in protective atmosphere are so incensed that at Ar; obtain N doping carbon compound; gained negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its method of testing is with embodiment 2.Test result is in table 1.
Although present invention has been description to a certain degree, significantly, under the condition not departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Be appreciated that and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the equivalent replacement of described each factor.
Claims (7)
1. a negative electrode active material, chemical formula is: [A
(x-y)b
y] [B
x/3ti
(1-x/3)] O
2-δ, wherein, A, B adopt Na and Li one wherein respectively; 0 < x≤1,0≤y < x, 0≤δ≤0.2.
2. negative electrode active material as claimed in claim 1, wherein, A is Na, B is Li; 0.5≤x≤0.8,0≤y < x, 0≤δ≤0.05.
3. negative electrode active material as claimed in claim 2, wherein, described negative electrode active material be coated with in carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer one or more; Wherein, the thickness of described carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer is 1 ~ 10nm independently of one another.
4. a negative material, described negative material comprises: the negative electrode active material as described in conductive additive, binding agent and employing are as arbitrary in claims 1 to 3.
5. a negative pole, described negative pole comprises negative material according to claim 4 and collector.
6. an alkali metal secondary battery, described alkali metal secondary battery comprises positive pole and negative pole according to claim 5, and is placed in the electrolyte between described positive pole and described negative pole.
7. the preparation method of negative electrode active material as claimed in claim 1 or 2, described preparation method is any one in solid phase method and sol-gel process:
Described sol-gel process comprises the steps:
1) take appropriate alkali-metal acetate and butyl titanate according to the stoichiometric proportion of negative electrode active material and be dissolved in absolute ethyl alcohol respectively, in whipping process, the ethanol solution of alkali metal acetate is slowly joined in the ethanol solution of butyl titanate, and add citric acid, form aqueous precursor gel;
2) gained aqueous precursor gel is placed in crucible in 250-500 DEG C of preliminary treatment two hours, then processes 8 ~ 20 hours at 750-1000 DEG C, grind and obtain described negative electrode active material;
Described solid phase method comprises the steps:
1) according to the stoichiometric proportion of negative electrode active material, by alkali-metal carbonate and titanyl compound mixing, after grinding evenly, precursor powder is obtained;
2) gained precursor powder is placed in crucible and processes 8 ~ 25 hours at 650 ~ 1000 DEG C, grind and obtain described negative electrode active material.
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Effective date of registration: 20180712 Address after: 100094 4 floor 258, block D, 24 building, 68 Beiqing Road, Haidian District, Beijing. Patentee after: Beijing Zhong Ke sea sodium Technology Co., Ltd. Address before: 100190 South Third Street, Zhongguancun, Haidian District, Haidian District, Beijing Patentee before: Research Institute of Physics, Chinese Academy of Sciences |
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