CN101222042B - Composition for negative electrode of non-aqueous rechargeable battery and non-aqueous rechargeable battery prepared by using same - Google Patents
Composition for negative electrode of non-aqueous rechargeable battery and non-aqueous rechargeable battery prepared by using same Download PDFInfo
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- CN101222042B CN101222042B CN2007101602944A CN200710160294A CN101222042B CN 101222042 B CN101222042 B CN 101222042B CN 2007101602944 A CN2007101602944 A CN 2007101602944A CN 200710160294 A CN200710160294 A CN 200710160294A CN 101222042 B CN101222042 B CN 101222042B
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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Abstract
The present invention relates to a negative material for a non-aqueous rechargeable battery and a non-aqueous rechargeable battery including the same. The negative material for a non-aqueous rechargeable battery includes lithium vanadium oxide that is obtained by mixing a lithium compound such as lithium carbonate (Li 2 CO 3 ) and a vanadium compound such as vanadium pentaoxide (V 2 O 5 ) with anorganic acid such as oxalic acid (COOH) 2 to obtain an organic acid salt precursor and firing the organic acid salt precursor. The negative material for a non-aqueous rechargeable battery can improvecharge and discharge characteristics of a non-aqueous rechargeable battery due to uniform composition.
Description
Technical field
The present invention relates to be used for such as the negative material of the non-aqueous rechargeable battery of Lithuim rechargeable battery and comprise the non-aqueous rechargeable battery of this negative material.The present invention relates more specifically to can improve because it is evenly formed the negative material that is used for non-aqueous rechargeable battery of non-aqueous rechargeable battery charge-discharge characteristic, and the non-aqueous rechargeable battery that comprises this improved negative material.
Background technology
Current lithium rechargeable battery comprises that the difference that is immersed in the nonaqueous electrolytic solution can embed and the positive pole of de-embedding lithium ion and negative pole (see on March 7th, 2003 disclosed exercise question be unsettled open No.2003-68305 claim 3-11 of Japan Patent and the accompanying drawing 10 of the Koji Yamamoto of " being used for secondary lithium battery cathode material and preparation method thereof " etc.).Comprise lithium-barium oxide in the described negative active core-shell material.The preparation of described lithium-barium oxide is to mix with solid phase method such as the lithium source of lithium hydroxide etc. with such as the vanadium source of vanadium trioxide etc., and is being not less than 650 ℃ or higher this mixture of roasting temperature.
When non-aqueous rechargeable battery charged, its negative pole was electronegative, embedded anodal lithium ion de-embedding and embedded negative pole subsequently.In addition, when non-aqueous rechargeable battery discharges, embed the lithium ion de-embedding of negative pole and embed anodal subsequently.
Measure the lithium standard open circuit potential of test battery, described test battery comprise lithium metal electrode and can according to current convention with the lithium-barium oxide sample of solid phase method preparation to electrode, described sample is by drying and mix lithium hydroxide and vanadium trioxide, then at 1100 ℃, roasting under the nitrogen atmosphere and making.
Yet when preparing lithium-barium oxide with seasoning, the composition of target material is inhomogeneous, and is difficult to the crystal structure that keeps stable.So, repeating charge and discharge cycles after-potential instability, so charge-discharge characteristic variation after repeating several times charge and discharge cycles.
Summary of the invention
So, an object of the present invention is to provide a kind of improved non-aqueous rechargeable battery.
Another object of the present invention provides a kind of negative material that is used for non-aqueous rechargeable battery.
Another purpose of the present invention provides a kind of negative material of homogeneous composition and non-aqueous rechargeable battery that a kind of use represents the negative material of homogeneous composition of representing.
A further object of the present invention provides a kind of at the negative material that has stabilizing potential after the continuous charge and discharge cycles and a kind of non-aqueous rechargeable battery that has the negative material of stabilizing potential after continuous charge and discharge cycles that uses.
An embodiment of the invention provide a kind of negative material that is used for non-aqueous rechargeable battery that improves the charge-discharge characteristic of non-aqueous rechargeable battery, and a kind of non-aqueous rechargeable battery that comprises described negative material.
An embodiment of the invention, can constitute by a kind of negative material that is used for non-aqueous rechargeable battery, it comprises lithium-barium oxide, wherein when lithium ion embedding and de-embedding, described open circuit potential (opencircuit potential) have potential change in 0.05V the stage of stable development, account for the entire reaction phase 25% or more, the wherein said stage of stable development has the average potential that the lithium ion in the scope between 0.20 to 0.25V embeds and the average potential of the lithium ion de-embedding in the scope between 0.23 to 0.27V.
The described negative material that is used for non-aqueous rechargeable battery has uniform composition, so it can improve the charge-discharge characteristic of non-aqueous rechargeable battery.
Description of drawings
With reference to hereinafter in conjunction with the accompanying drawings detailed description, more complete evaluation of the present invention and many thing followed advantages can become apparent and better understand, and wherein identical Reference numeral refers to identical composition, wherein:
Capacity and relation between the electromotive force two coordinate diagram of Fig. 1 for showing the negative material that is used for current non-aqueous rechargeable battery.
Fig. 2 is the longitudinal profile front view of the non-aqueous rechargeable battery of an execution mode structure of principle according to the present invention.
Fig. 3 is the two coordinate diagram that show according to the X-ray diffraction analysis result of the lithium-barium oxide of embodiment 1 and Comparative Examples 1.
Fig. 4 is two coordinate diagram of the partial enlarged drawing at the peak of embodiment 1 and Comparative Examples 1 (003) crystal face among Fig. 3.
Fig. 5 is two coordinate diagram of the relation between the discharge capacity of the negative material that is used for non-aqueous rechargeable battery of the function of the ratio of lithium used in the formation of explanation as acylate and vanadium.
Fig. 6 shows organic acid content used in the formation of acylate and is used for relation between the discharge capacity of negative material of non-aqueous rechargeable battery.
Fig. 7 shows capacity and the electromotive force (unit: the relation mAh/g) according to the negative material that is used for non-aqueous rechargeable battery of embodiment 1.
Embodiment
With reference now to accompanying drawing,, Fig. 1 shows the charge-discharge characteristic of current lithium-barium oxide negative material.As previously mentioned, when non-aqueous rechargeable battery charged, its negative pole was electronegative, embedded anodal lithium ion and also embedded negative pole subsequently from anodal de-embedding.In addition, when non-aqueous rechargeable battery discharged, the lithium ion that embeds negative pole was anodal from negative pole de-embedding and embedding subsequently.
The described test battery of lithium standard open circuit potential of measuring test battery comprise lithium metal electrode and with the conventional lithium-barium oxide sample of solid phase method preparation to electrode.The longitudinal axis is represented electromotive force, and (unit: V), trunnion axis is represented capacity (unit: mAh/g).Described sample is by dry and mix lithium hydroxide and vanadium trioxide, then at 1100 ℃, and roasting under the nitrogen atmosphere and making.
Among Fig. 1, A11 refers to that when non-aqueous rechargeable battery charged, its negative pole was electronegative, and when lithium ion embedded negative pole, embedded the first time of lithium ion, and B11 refers to that when non-aqueous rechargeable battery discharges lithium ion is from the de-embedding first time of negative pole.It is electronegative that A12 refers to work as negative pole, when lithium ion embeds negative pole, and the 10th embedding of lithium ion, B12 refers to 10th de-embedding of lithium ion from negative pole.
As shown in Figure 1, when lithium ion embeds (A11) negative pole and during for the first time from negative pole de-embedding (B11) for the first time, formation based on abscissa shown in the entire reaction phase less than 25%, the stage of stable development 100 of the variation of electromotive force in 0.05V, wherein said abscissa is defined as trunnion axis.That is to say, when lithium ion embeds in first circulation and the smooth electromotive force of demonstration during de-embedding.On the other hand, do not have the stage of stable development during embedding the 10th de-embedding (B12) of (A12) and lithium ion, this shows that its charge-discharge characteristic is undesirable the 10th time of lithium ion.
When preparing lithium-barium oxide with seasoning, the composition of target material is inhomogeneous, therefore is difficult to the crystal structure that keeps stable.Like this, repeating to discharge and recharge electromotive force instability afterwards, so the charge-discharge characteristic variation.
See the present invention now, the negative material that is used for non-aqueous rechargeable battery according to an execution mode makes up can prepare with the lithium-barium oxide that the acylate that comprises lithium and vanadium by roasting prepares.
The described negative material that is used for non-aqueous rechargeable battery comprises lithium-barium oxide, and described lithium-barium oxide comprises by roasting acylate precursor Li
aV
bM
cO
d(C
2O
4) Li that obtains
aV
bM
cO
dWherein M is an arbitrary element, and a, b, c and d are arbitrary value.
By lithium compound and vfanadium compound are mixed the acquisition acylate with organic acid.According to an execution mode, such as Li
aV
bM
cO
dC
2O
4Acylate by will be such as Li
2CO
3Lithium compound and such as V
2O
5Vfanadium compound together with such as (COOH)
2Organic acid mix and prepare.
(104) crystal face of the negative material that is obtained by above method compares in 0.2 to 0.8 scope with the peak intensity of (003) crystal face.According to another execution mode, the peak intensity of described (104) crystal face and (003) crystal face is than in 0.3 to 0.6 scope.Yet, when described peak intensity than less than 0.2 the time, the gained crystalline phase has problem, because the basal plane of the layering of mainly having grown and the prismatic surface growth is less.
According to an execution mode, be used in the scope of mol ratio between 1.2: 1 to 1.24: 1 of lithium and vanadium in lithium compound that the negative material of non-aqueous rechargeable battery mixes with organic acid and the vfanadium compound.
Further according to an execution mode, described organic acid amount is 1.5 to 5 times with the required mole of lithium compound and vfanadium compound reaction.
According to this execution mode, obtain acylate by following reaction equation 1 represented chemical reaction.The organic acid amount that this reaction spends is the X-Y mole, and the organic acid amount that offers reaction is the X mole.In addition, z is an arbitrary value.
[reaction equation 1]
0.22Li
2CO
3+V
2O
5+X(COOH)
2+zM→Li
aV
bM
cO
dC
2O
4+Y(COOH)
2 (1)
The negative material that is used for non-aqueous rechargeable battery according to an execution mode, lithium-barium oxide forms 25% or the more stage of stable development that accounts for along the circulation shown in the abscissa of containing entire reaction phase (trunnion axis), wherein when lithium ion embedded (A11) and de-embedding (B11) in first circulation, described electromotive force changed in the 0.05V scope.
The described stage of stable development has the average potential of scope at 0.20 to 0.25 V for embedding lithium ion, have scope 0.23 to 0.27 average potential for the de-embedding lithium ion.
According to this execution mode, measure charge-discharge characteristic with electrode that comprises the negative material that contains lithium-barium oxide and the test battery that contains lithium metal to electrode.This test battery demonstrates a smooth electromotive force when lithium ion embeds, wherein open circuit potential arrives in the scope of 0.25V 0.20 when lithium ion embeds.In addition, when the lithium ion de-embedding, this smooth electromotive force has the open circuit potential that arrives in the scope of 0.27V 0.23.Described smooth electromotive force has the stage of stable development, wherein said electromotive force account for that lithium ion embeds and the entire reaction phase of de-embedding 25% or more during in 0.05V, change.
At the negative material that is used for non-aqueous rechargeable battery that makes up according to execution mode, lithium ion embed for the first time with de-embedding after charge-discharge characteristic have the stage of stable development that accounts for based on 25% or more reversing of the abscissa of entire reaction phase.According to this execution mode, in the charge-discharge characteristic after circulation for the second time, when lithium ion embeds and during de-embedding, demonstrate the entire reaction phase 25% or more of accounting for, the stage of stable development that electromotive force changes in 0.05V.In addition, through whole circulation life-span almost, after the variation, the described stage of stable development may be shown as and account for below 25% of representing based on the abscissa of entire reaction phase of reaction cycle capacity.
According to another execution mode, be used for the negative material that is used for non-aqueous rechargeable battery of this execution mode, lithium ion embed for the first time with de-embedding after charge-discharge characteristic have 40% or the more stage of stable development that extends to the reaction cycle represented based on the abscissa of entire reaction phase.According to this execution mode, when lithium ion embedding and twice of de-embedding or more times circulation time, charge-discharge characteristic has the entire reaction of accounting for phase 40% or more, the stage of stable development that electromotive force changes in 0.05V.And in the cycle life through indicating, capacity is after the variation, the described stage of stable development may drop to contain based on the abscissa of entire reaction phase less than 40%.
According to the negative material that is used for non-aqueous rechargeable battery that comprises the lithium-barium oxide that is used for another execution mode, described charge-discharge characteristic has contains that lithium ion embeds or the abscissa 25% of the entire reaction phase of de-embedding or more, the stage of stable development of the maximum 0.05V of potential change, and this stage of stable development have 0.20 and 0.25V between the average potential that embeds of lithium ion, and 0.23 and 0.27V between the average potential of lithium ion de-embedding, and embed for the first time and de-embedding after charge-discharge characteristic have 25% or more stage of stable development of the abscissa of containing the entire reaction phase.
According to another execution mode, non-aqueous rechargeable battery comprises the negative pole that contains the negative material that is useful on non-aqueous rechargeable battery, positive pole and electrolyte.
According to an execution mode, the lithium-barium oxide that is used for non-aqueous rechargeable battery obtains by the acylate of roasting lithium and vanadium containing, so that uniform composition and stable structure to be provided.Therefore, it is more stable to discharge and recharge electromotive force, thereby improves charge-discharge characteristic.The vanadium source can comprise the cheap V that contains the pentavalent vanadium
2O
5Therefore can reduce and be used to produce negative material that non-aqueous rechargeable battery uses and the cost of producing non-aqueous rechargeable battery.
According to an execution mode, acylate can easily obtain by wet method, and in described wet method, lithium compound and vfanadium compound mix with organic acid and the described compound of roasting together.
Further, owing to be used for the lithium compound that mixes with organic acid and the mol ratio of vfanadium compound lithium and vanadium is adjusted between 1.2: 1 and 1.24: 1, thereby can provide and have the more non-aqueous rechargeable battery of high discharge capacity.
In another embodiment since organic acid with and lithium compound and vfanadium compound react amount between 1.5 to 5 times of required mole by excessive adding, therefore after roasting, can provide negative material with high discharge capacity.
According to another execution mode, the open circuit potential of negative material has a desirable stage of stable development.Because the embedding of the described stage of stable development for lithium ion has the average potential in the scope between 0.20 to 0.25V, and have the average potential in the scope between 0.23 to 0.27 for the de-embedding of lithium ion, therefore can provide and the close smooth electromotive force of electromotive force that contains the negative material of graphite.Therefore, owing to have the conventional negative material that contains graphite of lithium-barium oxide replacement of high power capacity with unit volume, thus obtained having the non-aqueous rechargeable battery of high-energy-density.
Further and since lithium ion embed for the first time with de-embedding after form stage of stable development of the abscissa at least 25% contain the entire reaction phase, therefore, but when negative pole repeats to discharge and recharge stabilizing potential and improve charge-discharge characteristic.
In addition, according to another execution mode,, still can significantly stablize described electromotive force even repeat to discharge and recharge; This stable be since lithium ion embed for the first time with de-embedding after in charge-discharge characteristic, form stage of stable development of at least 40% of the abscissa of containing the entire reaction phase.
Below, the non-aqueous rechargeable battery that makes up according to one embodiment of the present invention will be described with reference to the drawings.
Fig. 2 is the longitudinal profile front view according to the non-aqueous rechargeable battery of one embodiment of the present invention structure.This non-aqueous rechargeable battery 1 is the cylindrical battery of a screw winding.This non-aqueous rechargeable battery 1 comprises centrepin 6 and the electrode assemblie 10 of reeling around this centrepin 6.At this, this electrode assemblie 10 comprises anodal 3 and negative pole 4, and inserts anodal 3 and the dividing plate 5 of 4 at negative pole.Therefore, this electrode assemblie 10 has cylindrical structural.
Be arranged in by the anodal active piece 3a that will comprise positive electrode active materials and form anodal 3 on two surfaces of plus plate current-collecting body 3b.Be arranged in by the negative electrode active piece 4a that will comprise negative active core-shell material and form negative pole 4 on two surfaces of negative current collector 4b.Cylindrical electrode assembly 10 packed into to have in the hollow inner cylindrical shell 2, and injects electrolyte (not illustrating separately).Anodal 3 contact with shell 2, and have the positive terminal of giving prominence in shell 2 bottoms 7.
At electrode assemblie 10 tops and bottom insulation board 9b and 9a are housed.Plus plate current-collecting body 3b passes insulation board 9a and contacts with positive terminal 7 by positive wire 11.Guard plate 13 is installed on the insulation board 9b that is positioned at the cardinal extremity that shell 2 opens with the direction identical with insulation board 9b.Negative terminal 8 is configured as the shape of cap of projection, and is installed on the guard plate 13 with the direction opposite with guard plate 13.Negative current collector 4b passes insulation board 9b and contacts with negative terminal 8 by negative wire 12.And the packing ring 14 of the edge of negative terminal 8 and guard plate 13 usefulness electric insulations seals, and guard plate 13 and negative terminal 8 are separated with positive terminal 7.
Positive electrode active materials and electrolyte can comprise common positive electrode active materials and the electrolyte that is used for non-aqueous rechargeable battery.For example, positive electrode active materials can comprise lithium transition elements oxide such as lithium and cobalt oxides etc.Electrolyte can be included in to contain in the solvent such as ethylene carbonate, diethyl carbonate etc. and be selected from by LiPF
6, Li
2SiF
6, Li
2TiF
6, LiBF
4Solution Deng the lithium salts in the group of being formed.
Lithium-barium oxide by roasting under such as the atmosphere of nitrogen by Li
aV
bM
cO
d(C
2O
4) expression acylate and obtain.
For example, can be by making such as lithium carbonate (Li
2CO
3) lithium compound, such as vanadic oxide (V
2O
5) vfanadium compound and such as oxalic acid ((COOH)
2) organic acid in the aqueous solution, react, obtain described acylate by evaporation drying then.
And, when using lithium carbonate, vanadic oxide and oxalic acid, can greatly reduce cost, and can obtain acylate.Described lithium compound can comprise lithium hydroxide or lithium oxalate.Organic acid can comprise acetic acid, citric acid, malic acid or butanedioic acid except that oxalic acid.
According to described manufacture method, by roasting wherein the acylate that tentatively mixed of lithium atom and vanadium atom obtain lithium-barium oxide.Compare with the conventional lithium-barium oxide that lithium compound and vfanadium compound mixing and roasting is obtained, in enforcement of the present invention, lithium and vanadium atom tend to micron order by solid solution equably.Therefore, can provide lithium-barium oxide with even composition.
Following examples will illustrate in greater detail principle of the present invention.Yet, be understood that the present invention is not limited to these embodiment.
The preparation of embodiment 1. lithium-barium oxides
With lithium carbonate Li
2CO
3Lithium compound, vanadic oxide V
2O
5Vfanadium compound and oxalic acid (COOH)
2Organic acid in the aqueous solution, mix and react, evaporate then so that acylate Li to be provided
aV
bM
cO
dC
2O
4The lithium of lithium carbonate and vanadic oxide and the mol ratio of vanadium are 1.22: 1, and organic acid adds with 1.5 times the amount that itself and lithium carbonate and vanadic oxide react required mole.
The acylate precursor of gained is at 1100 ℃, and roasting is to obtain lithium-barium oxide under the nitrogen atmosphere.
The preparation of embodiment 2. lithium-barium oxides
Prepare lithium-barium oxide according to the process identical with embodiment 1, difference is to replace oxalic acid with citric acid.
Comparative Examples 1
According to solid phase method with 26.35gLiOH and 67.5g V
2O
3Mix, and 650 ℃ of roastings so that lithium-barium oxide to be provided.
Lithium-barium oxide according to embodiment 1 and Comparative Examples 1 preparation carries out X-ray diffraction analysis.The results are shown in Fig. 3 and 4.
Fig. 3 shows that Fig. 4 is the partial enlarged drawing at the peak of (003) shown in Figure 3 crystal face according to the collection of illustrative plates of the X-ray diffraction analysis of the lithium vfanadium compound of embodiment 1 and Comparative Examples 1.
Shown in Fig. 3 and 4, be 0.6 according to the peak intensity ratio of (104) crystal face of the lithium-barium oxide of embodiment 1 preparation and (003) crystal face, on the other hand, be 0.3 according to the peak intensity ratio of (104) crystal face of the lithium-barium oxide of Comparative Examples 1 preparation and (003) crystal face.
For embodiment 3, with 80wt% by embodiment 1 preparation lithium-barium oxide, the acetylene black of 10wt% and the polyvinylidene fluoride of 10wt% mix, and are coated in then on the negative current collector that comprises copper.The negative current collector of this coating is depressed into 1.8g/cm then
3So that negative pole to be provided.
LiCoO with 91wt%
2Positive electrode active materials, the acetylene black of 3wt% and the polyvinylidene fluoride of 6wt% mix so that positive electrode to be provided.So the solvent of non-aqueous electrolytic solution comprises EC: (ethylene carbonate: diethyl carbonate)=3: 7 (volume ratio), electrolyte comprises LiPF to DEC
6
Then, electrolyte solution is injected described electrode assemblie, and after making battery place 1 hour sealed entry, so that lithium rechargable battery to be provided.
Make lithium rechargable battery according to the method identical with embodiment 3, difference is the lithium-barium oxide that adopts according to embodiment 2.
In embodiment 4, prepare lithium-barium oxide according to the process identical with embodiment 1, difference is to change and inserts (COOH)
2In Li
2CO
3And V
2O
5The mol ratio of middle lithium and vanadium, or in the different samples of embodiment 4, change the organic acid addition.Then, this lithium-barium oxide is used for electrode, and lithium metal is used for electrode, so that the test battery with lithium standard open circuit potential to be provided.Measure the charge/discharge capacity of this battery.The results are shown in Fig. 5 and 6.
In Fig. 5 and 6, the ordinate or the longitudinal axis are represented the discharge capacity (unit: mAh/g) of test battery.In Fig. 5, abscissa or trunnion axis represent to insert (COOH)
2In Li
2CO
3And V
2O
5The mol ratio of middle lithium and vanadium.Organic acid adds with 1.5 times the amount that itself and lithium carbonate and vanadic oxide react required mole.
As shown in Figure 5, work as Li
2CO
3In lithium and V
2O
5In the mol ratio of vanadium at 1.2: 1 between 1.24: 1 the time, can increase discharge capacity.
So, the trunnion axis of Fig. 6 represent with ratio represent at Li
2CO
3, V
2O
5(COOH)
2Reaction in (COOH) that exist
2Amount, (COOH) that wherein spends
2Amount count 1.In other words, acylate Li
aV
bM
cO
dC
2O
4By reaction equation 1 expression, (COOH) that in this reaction, spends
2Amount be the X-Y mole.In Fig. 6, abscissa or trunnion axis are represented the ratio of X/ (X-Y).In addition, z is an arbitrary value.
1.22Li
2CO
3+V
2O
5+X(COOH)
2+zM→Li
aV
bM
cO
d?C
2O
4+Y(COOH)
2 (2)
As shown in Figure 6, if (COOH)
2With itself and Li
2CO
3And V
2O
5The amount of reacting between 1.5 to 5 times of required mole exists, and high discharge capacity can be provided.
Mensuration is according to the charge-discharge characteristic of the lithium-barium oxide of the negative material of embodiment 1.The results are shown in Fig. 7.
Test battery comprise lithium metal electrode and according to the lithium-barium oxide of embodiment 1 to electrode, and be used to measure lithium standard open circuit potential.The longitudinal axis represents that (unit: V), trunnion axis is represented capacity (unit: mAh/g) to electromotive force.Insert (COOH)
2In Li
2CO
3In the lithium and the V that contain
2O
5In the mol ratio of the vanadium that contains be 1.22: 1.
As shown in Figure 7, A1 represents the electromotive force under the lithium ion embedding situation for the first time.B1 represents the electromotive force under the lithium ion de-embedding for the first time situation.A2 represents that electromotive force under the 10th embedding situation of lithium ion and B2 represent the electromotive force under the 10th de-embedding situation of lithium ion.
As shown in Figure 7, in the test battery that comprises according to the lithium-barium oxide of embodiment 1, when lithium ion the 1st and the 10th time embed A1 and A2, and when the 1st and the 10th de-embedding B1 and B2, wherein described stage of stable development of in 0.05V, changing of electromotive force account for the entire reaction phase 70% or more.When lithium embedded, the described stage of stable development had the smooth electromotive force of the about 0.22V of average potential, and when the lithium de-embedding, the described stage of stable development has the smooth electromotive force of the about 0.25V of average potential.
As shown in Figure 1, in the test battery that adopts the conventional lithium-barium oxide for preparing by solid phase method, when embed A11 and de-embedding B11 the first time of lithium ion, form the stage of stable development.Yet, when lithium ion embeds A12 and de-embedding B12 the 10th time, do not form the stage of stable development.
Think that producing such result is because lithium-barium oxide has homogeneous granules composition and stable crystal structure.Therefore, can provide and have the stable non-aqueous rechargeable battery that discharges and recharges electromotive force 1.In addition, in lithium-barium oxide, when the embedding second time of lithium ion and de-embedding, do not form the stage of stable development by the solid phase method preparation.
When inserting (COOH)
2In Li
2CO
3In the lithium and the V that contain
2O
5In the vanadium that contains when providing with the larger proportion between 1.2: 1 and 1.24: 1, demonstrate smooth electromotive force shown in Figure 5.In for this scope that obtains high discharge capacity, the described stage of stable development has 0.20 to 0.25V smooth electromotive force when lithium ion embeds, and the described stage of stable development has 0.23 to 0.27V smooth electromotive force when the lithium ion de-embedding.
In lithium-barium oxide according to an execution mode, when further repeating to discharge and recharge, the rapid variation of capacity.When the cycle life variation to total capacity 50% the time, during entire reaction, 25% form the stage of stable development.When 20% or the stage of stable development formed more during entire reaction, do not cause damage substantially.When 25% or when formed more, can provide enough substantially performances.In addition, when 40% or described stage of stable development formed more during entire reaction, can provide the non-aqueous rechargeable battery of quite stable.
According to an execution mode, the lithium-barium oxide that contains in the negative pole 4 obtains by the acylate of roasting lithium and vanadium containing, and roasting is evenly carried out like this, and crystal structure becomes stable.Therefore, the electromotive force that discharges and recharges of non-aqueous rechargeable battery 1 becomes stable to improve charge-discharge characteristic.
When passing through with Li
2CO
3And V
2O
5With (COOH)
2Mix when obtaining acylate described acylate Li
aV
bM
cO
dC
2O
4Easily obtain by wet method.Described lithium source can comprise another kind of lithium compound, and described vanadium source can comprise another kind of vfanadium compound.In addition, also can comprise except that (COOH)
2Outside organic acid.
According to conventional methods, because lithium-barium oxide contains the vanadium of trivalent or tetravalence, thereby need expensive V
2O
3Or V
2O
4As the vanadium source.Yet,, in wet method, contain the V of pentavalent vanadium according to an embodiment of the invention
2O
5Be reduced into trivalent or tetravalence vanadium.Therefore, because with cheap V
2O
5Replaced expensive vanadium source, at the preparation negative material or comprise in the non-aqueous rechargeable battery of this negative material and saved cost.
Because the charge-discharge characteristic of described negative material has the stage of stable development, the described stage of stable development embeds for lithium ion and has 0.20 average potential that arrives in the 0.25V scope, and have 0.23 average potential in the 0.27V scope for the described stage of stable development of the de-embedding of lithium ion, formed near the smooth electromotive force that contains the conventional negative material of graphite.Therefore, the lithium-barium oxide that has high power capacity with unit volume replaces conventional negative material, and the non-aqueous rechargeable battery with high-energy-density can be provided.
The present invention is in conjunction with thinking that at present practical illustrative embodiments is described, yet should understand the present invention and be not limited to disclosed execution mode, on the contrary, the invention is intended to cover the interior various variations and the equivalent arrangements of spirit and scope of claims.
Claims (16)
1. a negative material that is used for non-aqueous rechargeable battery comprises by roasting comprising the lithium-barium oxide that the acylate of lithium and vanadium obtains,
Wherein said lithium-barium oxide has open circuit potential, and described open circuit potential has 25% or the more stage of stable development of the entire reaction phase of the embedding that accounts for lithium ion or de-embedding;
Wherein when lithium electrode was recharged and discharge, the described stage of stable development changed in 0.05V; And
The wherein said stage of stable development has 0.20 and arrives the average potential of the lithium ion embedding in the 0.25V scope and arrive the average potential of the lithium ion de-embedding in the 0.27V scope 0.23.
2. the negative material that is used for non-aqueous rechargeable battery according to claim 1, wherein first time of lithium ion embed and de-embedding after, the stage of stable development described in the charge-discharge characteristic based on the entire reaction phase 25% or more during formation.
3. the negative material that is used for non-aqueous rechargeable battery according to claim 1, wherein first time of lithium ion embed and de-embedding after, the stage of stable development described in the charge-discharge characteristic based on the entire reaction phase 40% or more during formation.
4. the negative material that is used for non-aqueous rechargeable battery according to claim 1:
Wherein said lithium-barium oxide has open circuit potential, and described open circuit potential has 25% or the more stage of stable development of the entire reaction phase of the embedding that accounts for lithium ion or de-embedding;
Wherein when described lithium electrode was recharged and discharges, the described stage of stable development changed in 0.05V;
The wherein said stage of stable development has 0.20 and arrives the average potential of the lithium ion embedding in the 0.25V scope and arrive the average potential of the lithium ion de-embedding in the 0.27V scope 0.23; And
Wherein after the embedding first time of lithium ion and de-embedding, the described stage of stable development is forming based on 25% during the entire reaction of charge-discharge characteristic or more.
5. the negative material that is used for non-aqueous rechargeable battery according to claim 1, wherein said acylate obtains by lithium compound and vfanadium compound are mixed with organic acid.
6. the negative material that is used for non-aqueous rechargeable battery according to claim 5, wherein the mol ratio of lithium that contains in lithium compound that mixes with described organic acid and the vfanadium compound and vanadium is in 1.2: 1 to 1.24: 1 scope.
7. the negative material that is used for non-aqueous rechargeable battery according to claim 6, wherein said organic acid adds with 1.5 to 5 times amount with the required mole of described lithium compound and vfanadium compound reaction.
8. the negative material that is used for non-aqueous rechargeable battery according to claim 1, wherein said negative material have the peak intensity ratio of (104) crystal face in 0.2 to 0.8 scope and (003) crystal face.
9. non-aqueous rechargeable battery comprises:
Negative pole;
Anodal; With
Electrolyte;
Wherein said negative pole comprises by roasting and comprises the lithium-barium oxide that the acylate of lithium and vanadium obtains, described lithium-barium oxide has open circuit potential, and described open circuit potential has 25% or the more stage of stable development of the entire reaction phase of the embedding that accounts for lithium ion or de-embedding;
Wherein when lithium electrode was recharged and discharge, the described stage of stable development changed in 0.05V; And
The wherein said stage of stable development has 0.20 and arrives the average potential of the lithium ion embedding in the 0.25V scope and arrive the average potential of the lithium ion de-embedding in the 0.27V scope 0.23.
10. non-aqueous rechargeable battery according to claim 9, wherein first time of lithium ion embed and de-embedding after, the described stage of stable development based on entire reaction phase of charge-discharge characteristic 25% or more during formation.
11. non-aqueous rechargeable battery according to claim 9, wherein after the embedding first time of lithium ion and de-embedding, the described stage of stable development is forming based on 40% during the entire reaction of charge-discharge characteristic or more.
12. non-aqueous rechargeable battery according to claim 9:
Wherein said lithium-barium oxide has open circuit potential, and described open circuit potential has 25% or the more stage of stable development of the entire reaction phase of the embedding that accounts for lithium ion or de-embedding;
Wherein when described lithium electrode was recharged and discharges, the described stage of stable development changed in 0.05V;
The wherein said stage of stable development has 0.20 and arrives the average potential of the lithium ion embedding in the 0.25V scope and arrive the average potential of the lithium ion de-embedding in the 0.27V scope 0.23; And
Wherein after the embedding first time of lithium ion and de-embedding, the described stage of stable development is forming based on 25% during the entire reaction of charge-discharge characteristic or more.
13. non-aqueous rechargeable battery according to claim 9, wherein said acylate obtains by lithium compound and vfanadium compound are mixed with organic acid.
14. non-aqueous rechargeable battery according to claim 13, wherein the mol ratio of lithium that contains in lithium compound that mixes with described organic acid and the vfanadium compound and vanadium is in 1.2: 1 to 1.24: 1 scope.
15. non-aqueous rechargeable battery according to claim 13, wherein said organic acid adds with 1.5 to 5 times amount with the required mole of described lithium compound and vfanadium compound reaction.
16. non-aqueous rechargeable battery according to claim 9, wherein said negative material have the peak intensity ratio of (104) crystal face in 0.2 to 0.8 scope and (003) crystal face.
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|---|---|---|---|
| JP2006339508A JP5270089B2 (en) | 2006-12-18 | 2006-12-18 | Method for producing negative electrode material for non-aqueous secondary battery and method for producing non-aqueous secondary battery using the same |
| JP2006-339508 | 2006-12-18 | ||
| JP2006339508 | 2006-12-18 | ||
| KR1020070120974A KR101009623B1 (en) | 2006-12-18 | 2007-11-26 | Composition for negative electrode of non-aqueous secondary battery and non-aqueous secondary battery prepared by using same |
| KR1020070120974 | 2007-11-26 | ||
| KR10-2007-0120974 | 2007-11-26 |
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| CN101222042B true CN101222042B (en) | 2010-06-02 |
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|---|---|
| JP (1) | JP5270089B2 (en) |
| KR (1) | KR101009623B1 (en) |
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| KR101305958B1 (en) * | 2011-07-19 | 2013-09-12 | 전자부품연구원 | Negative Electrode Material For Lithium Secondary Battery Using Lithium-Vanadium Complex Oxide And Manufacturing Method Thereof |
| CN102509783A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Microwave hydrothermal preparation method of positive electrode material LiV3O8 of lithium battery |
| KR101623720B1 (en) | 2013-03-15 | 2016-05-26 | 주식회사 엘지화학 | Anode Active Material with High Capacity and Secondary Battery Comprising the Same |
| KR101528333B1 (en) | 2013-06-07 | 2015-06-15 | 한국과학기술연구원 | Sodium Vanadium Oxide Anode Material for Sodium Ion Secondary Battery, Preparation Method Thereof and Sodium Ion Secondary Battery Having the same |
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| Publication number | Publication date |
|---|---|
| JP5270089B2 (en) | 2013-08-21 |
| KR101009623B1 (en) | 2011-01-21 |
| CN101222042A (en) | 2008-07-16 |
| KR20080056637A (en) | 2008-06-23 |
| JP2008153045A (en) | 2008-07-03 |
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