CN100344018C - Method for regulating terminal voltage of cathode during overdischarge and cathode active material for lithium secondary battery - Google Patents
Method for regulating terminal voltage of cathode during overdischarge and cathode active material for lithium secondary battery Download PDFInfo
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- CN100344018C CN100344018C CNB200480003043XA CN200480003043A CN100344018C CN 100344018 C CN100344018 C CN 100344018C CN B200480003043X A CNB200480003043X A CN B200480003043XA CN 200480003043 A CN200480003043 A CN 200480003043A CN 100344018 C CN100344018 C CN 100344018C
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Abstract
Disclosed is a method for regulating terminal voltage of a cathode during overdischarge. Also disclosed is a lithium secondary battery, which is low in capacity loss after overdischarge, having excellent capacity restorability after overdischarge and shows an effect of preventing a battery from swelling at a high temperature.
Description
Technical field
The present invention relates to a kind of method of negative electrode final voltage when regulating overdischarge.The invention still further relates to lithium secondary battery, its capacitance loss after overdischarge is low, has good capacity restorability after overdischarge, and has the performance that prevents that battery from high temperature expanding.
Background technology
In recent years, the development in every technology along with mobile communication industry and information electronic industry increases day by day to the demand of low weight, lithium secondary cell with high capacity.But lithium secondary battery is overcharging or owing to discharge excessive heat burning and blast can take place during short-circuit condition.In addition, when lithium secondary battery is overdisharged to when being lower than its normal voltage scope, its capacity can obviously be reduced, and has hindered subsequent applications.
Owing to these reasons, since the exploitation first of lithium secondary battery quilt, safety device such as protective circuit, PTC element etc. have been connected on the lithium secondary battery always.But this class protective circuit, PTCs etc. are not preferred, because they are relatively more expensive and occupied larger volume, thereby have increased battery cost, volume and weight.Therefore, be starved of the battery of low manufacturing cost and high battery capacity, and do not use described protective circuit, PTC etc.
Usually, overcharging or safety during short circuit, be used in the organic or inorganic additive in the nonaqueous electrolyte or change the external structure of battery in order to ensure battery.But when battery is overdisharged to appropriate voltage when following, even attempt to charge once more, battery capacity is significantly reduced, makes battery no longer can be recharged/discharge.
Kai Fa conventional lithium secondary battery has such structure so far, and discharge is subjected to the restriction and the termination of anode when making overdischarge.Especially, when non-aqueous lithium secondary battery during, formed solid electrolyte interface (SEI) film at anode surface by initial charge.At this moment, used a large amount of lithium ions that discharge from negative electrode, thereby the amount that participates in the Li of charge/discharge is reduced.When overdischarge occurs under the situation that the amount of Li is reduced, the activated li site on the negative electrode can not fully be occupied, thereby cathode voltage is not reduced to certain below the voltage.Therefore, discharge is stopped (see figure 1) by anode.
Simultaneously, battery capacity is owing to following reason is significantly reduced.Cell voltage is defined as poor between cathode voltage and the anode voltage.In addition, even after cell voltage was reduced to below the conventional working voltage, battery is still continuous discharge under low current.At this moment, owing to consumed the Li ion of anode, cathode voltage no longer reduces, thereby it is slowly reduced.On the other hand, anode voltage increases fast, rises to 3.6V at last, and is oxidized at this copper coil as anode collector.Therefore, copper coil is dissolved with the copper ion form, thereby has polluted electrolyte.Then, when battery charge, copper ion is attached to anode surface once more, thereby active material of positive electrode becomes and can not use.Therefore, if the copper coil oxidation takes place, battery capacity descends fast after the overdischarge, thereby battery becomes and can not use.
Thereby, needing the such battery of exploitation, its discharge is limited by anode, thus battery capacity is not significantly reduced after the overdischarge.In addition, be starved of the new method of the limited battery of this class negative electrode of preparation.
Summary of the invention
As mentioned above, when overdischarge takes place, just produce such problem, promptly having relative anode voltage than high irreversible capacity increases fast, and copper ion dissolves from anode collector, thereby charge/discharge cycle can not successfully be carried out.Anode voltage increases when preventing overdischarge, needs to increase the irreversible capacity of negative electrode with faster reduction cathode voltage.In order to increase the irreversible capacity of negative electrode, the present invention adopts to negative electrode and adds the additive with high irreversible capacity.
We find, when the lithium nickel oxide by following general formula 1 expression is used as the cathode active material feed additives, take place to change mutually with the irreversible reaction in control cathode and the anode in lithium nickel oxide, thereby battery capacity can obviously not reduce after the overdischarge.
Therefore, obtain the present invention based on this discovery.An object of the present invention is to provide a kind of battery, its discharge is limited by negative electrode, used to comprise the lithium nickel oxide active material of cathode of being represented by following general formula 1 as additive, thereby battery capacity can significantly not reduce after the overdischarge.
Simultaneously, lithium nickel oxide at high temperature can cause cell expansion according to its addition.About this point, we find when the lithium nickel oxide (wherein nickel is partly replaced by other element) by following general formula 1 expression is used as the cathode active material feed additives, battery capacity is not significantly reduced after the overdischarge, the overall performance that keeps battery simultaneously, and, it has good capacity restoration performance after the overdischarge, and can prevent that battery from high temperature expanding.We also find, when being used as the cathode active material feed additives by the lithium nickel oxide of following general formula 1 expression of the oxide-coated beyond the lithium nickel oxide, battery capacity is not significantly reduced after the overdischarge, the overall performance that has kept battery simultaneously, in addition, also can after overdischarge, obtain good capacity restoration performance in this case, and can prevent that battery from high temperature expanding.
According to an aspect of the present invention, provide a kind of in the overdischarge process when electrical potential difference (voltage) between negative electrode and anode when the 0V, regulate the method for lithium secondary battery negative electrode final voltage, it comprises by adding second kind of lithium transition-metal oxide to the active material of cathode that contains first kind of lithium transition-metal oxide that can embedding/lithium ionic insertion/deinsertion and forms negative electrode as additive, and wherein second kind of lithium transition-metal oxide irreversible capacity (1-discharge capacity/charging capacity) in first time charge/discharge cycle is greater than first kind of lithium transition-metal oxide.
According to another aspect of the present invention, a kind of active material of cathode that is used for lithium secondary battery is provided, it contains the lithium transition-metal oxide of enough embedding/lithium ionic insertion/deinsertions, and it comprises that also the wherein nickel of following general formula 1 expression is partly replaced the lithium nickel oxide of (prerequisite is that y is not 0) by other element; Perhaps general formula 1 expression and lithium nickel oxide that applied by the oxide surface beyond the lithium nickel oxide is as additive:
[general formula 1]
Li
2+xNi
1-yM
yO
2+a
Wherein, x is the number of satisfied-0.5≤x≤0.5, y is the number that satisfies 0≤y＜1, and a is the number that satisfies 0≤a＜0.3, and M is at least a element that is selected from P, B, C, Al, Sc, Sr, Ti, V, Zr, Mn, Fe, Co, Cu, Zn, Cr, Mg, Nb, Mo and Cd.
According to a further aspect of the invention, it provides a kind of lithium secondary battery that comprises above-mentioned active material of cathode.
Lithium secondary battery of the present invention comprises: (a) contain the negative electrode of active material of cathode of the present invention, (b) anode, (c) slider and (d) contain the nonaqueous electrolyte of lithium salts and electrolyte compound.
Hereinafter will elaborate the present invention.
Lithium nickel oxide as cathode active material feed additives of the present invention is represented with following general formula 1:
[general formula 1]:
Li
2+xNi
1-yM
yO
2+a
Wherein, x is the number of satisfied-0.5≤x≤0.5, y is the number that satisfies 0≤y＜1, and a is the number that satisfies 0≤a＜0.3, and M is at least a element that is selected from P, B, C, Al, Sc, Sr, Ti, V, Zr, Mn, Fe, Co, Cu, Zn, Cr, Mg, Nb, Mo and Cd.
Preferably, be oxide or the composite oxides that are selected from least a element of Al, Mg, Si, P, C, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Zr and Nb as the oxide beyond the lithium nickel oxide of the lithium nickel oxide face coat of general formula 1 expression.The object lesson of described oxide or composite oxides comprises Al
2O
3, ZrO
2, AlPO
4, SiO
2, TiO
2And MgO, but be not limited in this.
Compound by general formula 1 expression preferably belongs to space group Immm.More preferably, in the stereochemical structure of compound, the Ni/M composite oxides form four-coordination planar structure (Ni, M) O
4, and two four-coordination planar structures that face with each other have a common face (being formed by O-O), thus form main chain on the whole.In addition, the compound of general formula 1 expression preferably has following lattice constant: a=3.7+0.5 , b=2.8+0.5 , c=9.2+0.5 , α=90 ° wherein, β=90 ° and γ=90 °.
Shown in Fig. 6～9, the lithium nickel oxide that the wherein nickel of general formula 1 expression is partly replaced by other element has and Li
2NiO
2(Fig. 9) similar x-ray diffraction pattern (Fig. 6～8).Although this shows that the nickel in the lithium nickel oxide is partly replaced by other element, lithium nickel oxide structurally can not change.
In the structure of the compound of general formula 1 expression, in the charge/discharge cycle embedding/lithium ionic insertion/deinsertion takes place in the first time, wherein the oxidation number of Ni or M from+2 become+4, Li
2+xNi
1-yM
yO
2+aStructure Li takes place to be transformed into mutually
2+x-zNi
1-yM
yO
2(wherein 0≤z≤2).
For example, LiNiO
2Have the lattice structure that belongs to space group R3-m (trigonal system hexagonal crystal system), a=b wherein, promptly a is identical with b, and c is different with them, α=β=90 ° and γ=120 °.
The compound of general formula 1 expression is deviate from least 1 mole lithium ion in the first time in the charging cycle process, and still, in first time discharge cycles process or afterwards, it becomes can embedding/take off 1 mole or the material of lithium ion still less.
For example, at Li
2NiO
2Situation under, with LiNiO
2Difference is supplied to anode in 1 mole of when charging or more lithium ion, and 1 mole or lithium ion are still less received by negative electrode when discharge.Therefore, Li in the charge/discharge cycle first time
2NiO
2Discharging efficiency (discharge capacity/first time charging capacity * 100 for the first time) be about 40% or still less.At general formula 1:Li
2+xNi
1-yM
yO
2+aUnder the situation of the compound of expression, the efficient of charge/discharge is slightly different with the amount of the metal M that replaces Ni for the first time.
Correspondingly, when the lithium nickel oxide by general formula 1 expression was used in the negative electrode additive as active material of cathode, cathode active material feed composition of the present invention had very big difference between initial charge capacity and initial discharge capacity.This irreversible capacity provides the lithium ion of such amount at least, when charging for the first time with compensation since on anode surface formation SEI film cause irreversibly consuming in the anode reaction of lithium.Therefore, it can compensate the high irreversible capacity of anode in the charge/discharge cycle process first time.
In addition, the capacity that cathode active material feed composition of the present invention can suppress to cause owing to overdischarge reduces, it has utilized the irreversibility at the lithium nickel oxide of the charge/discharge cycle formula of 1 expression first time, wherein the cathode active material feed composition comprise can embedding/lithium ionic insertion/deinsertion lithium transition-metal oxide and the lithium nickel oxide of general formula 1 expression.Described mechanism such as Fig. 1.
Cell voltage is defined as the electrical potential difference between negative electrode and anode.Battery over-discharge continues to carry out, and becomes 0V up to cell voltage, and is identical at the electromotive force of this point cathode and anode.
As mentioned above, usually when overdischarge took place, having relative anode voltage than high irreversible capacity increased fast, thereby copper ion stripping from the anode collector makes charge/discharge cycle successfully not carry out.Above-mentioned overdischarge problem causes being usually less than as the irreversibility of the lithium transition-metal oxide of active material of cathode the irreversibility of carbon-based anode active material.Anode voltage increases when preventing overdischarge, needs to increase the irreversible capacity of negative electrode, with quick reduction cathode voltage.In order to increase the irreversible capacity of negative electrode, the present invention has adopted to negative electrode and has added the additive with high irreversible capacity.
According to the present invention, the negative electrode of lithium secondary battery is to form as additive by adding second kind of lithium transition-metal oxide to the active material of cathode that contains first kind of lithium transition-metal oxide that can embedding/lithium ionic insertion/deinsertion, and wherein second kind of lithium transition-metal oxide irreversible capacity (1-discharge capacity/charging capacity) in first time charge/discharge cycle is higher than the irreversible capacity of first kind of lithium transition-metal oxide.Thereby, in the overdischarge process, when the electrical potential difference between negative electrode and anode (voltage) is 0V, can regulate the final voltage of negative electrode.
For the first time the irreversible capacity of additive should be greater than 4% during charge/discharge cycle, that is, and and the irreversible capacity of conventional active material of cathode.The irreversible capacity of additive is preferably 30% or higher.
In addition, in order to reduce the consumption of additive, the irreversible capacity of preferable additives (actual capacity itself, rather than the ratio of capacity) is higher relatively.
Preferably, the consumption of additive can irreversibly provide at least the lithium ion of amount like this, when charging for the first time with compensation because the reaction that causes in anode, irreversibly consuming lithium at formation SEI film on the anode surface.Because the irreversible capacity of anode is generally 8%, the preferred irreversible capacity of additive is 8% or higher, to reduce the consumption of additive.
According to the present invention; when the compound that adds general formula 1 expression to negative electrode extremely can compensate the irreversible capacity of anode; in the over-discharge test of SCF (safety circuit free does not have protective circuit) battery, can obtain very good performance, this circuit that do not need protection.Recently, described SCF battery receives the very big concern of battery manufacturers.
Simultaneously, the negative electrode that is added to lithium secondary battery when lithium nickel oxide is during as the additive of active material of cathode, can be when the charging and the electrolyte generated reactive gas with the Ni that+4 valency oxidation state are present in the lithium nickel oxide.Therefore, the addition battery that depends on lithium nickel oxide at high temperature may expand.But, because the ionic conductivity of non-aqueous lithium secondary battery is low, so anode should closely contact to each other with negative electrode.Therefore when battery expanded, the exposure level between anode and negative electrode descended, thereby has increased resistance.
In order to solve this class problem, the invention provides a kind of active material of cathode that is used for lithium secondary battery, its contain can embedding/lithium ionic insertion/deinsertion lithium transition-metal oxide, it comprises that also the wherein nickel of general formula 1 expression is partly replaced the lithium nickel oxide of (prerequisite is that y is not 0) by other element, or general formula 1 expression and lithium nickel oxide that applied by the oxide surface beyond the lithium nickel oxide is as additive.
The compound of general formula 1 expression can make salt, slaine, organic-metallic salt by the reaction method as solid phase reaction, coprecipitation and sol-gel process or be selected from the oxide of at least a element of P, B, C, Al, Sc, Sr, Ti, V, Zr, Mn, Fe, Co, Cu, Zn, Cr, Mg, Nb, Mo and Cd and lithium salts and nickel salt react and obtain.Also can use said method method in addition to prepare the compound of general formula 1 expression.
In addition, cathode active material feed additives of the present invention can obtain by the lithium nickel oxide that applies general formula 1 (comprising y=0) expression with the oxide surface beyond the lithium nickel oxide, for example is selected from the oxide or the composite oxides of at least a element of Al, Mg, Si, P, C, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Zr and Nb.Above-mentioned surface-coated can prevent the Ni that exists with+4 valency oxidation state and electrolyte reaction, thereby prevents the gas generation that causes because of Ni and electrolyte reaction.Therefore, can prevent that battery from high temperature expanding.
The lithium nickel oxide of representing with the general formula 1 of the coating of the oxide surface beyond the lithium nickel metal oxide can obtain by the lithium nickel oxide of representing with the solution surface coating general formula 1 of the salt, slaine or the organic metal salt that contain at least a element that is selected from Al, Mg, Si, P, C, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Zr and Nb, and it mixes with the sol-gel form or is dissolved in organic solvent or the water.
The surface-coated method can comprise the precipitation method, filtration method, boulton process, CVD (ChemicalVapor Deposition chemical vapour deposition technique), sputtering method etc., but is not limited thereto.The precipitation method are undertaken by lithium nickel oxide is introduced in the solution that contains compound, described compound contains at least a element that is selected from Al, Mg, Si, P, C, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Zr and Nb, for example aluminium isopropoxide, propyl alcohol zirconium, aluminum nitrate, magnesium acetate etc., it mixes with the sol-gel form or is dissolved in organic solvent or the water, thereby can obtain to precipitate slurry.Filtration method is realized by using the vacuum filter separating slurry.In addition, boulton process is to realize by solvent contained in the bone dry slurries in vacuum desiccator.
The additive that is used for active material of cathode of the present invention, based on 100 weight portion active material of cathode, its preferable amount is 0.1～10 weight portion.When the active material of cathode content of additive was 0.1 weight portion, in the overdischarge experiment, anode voltage increased before cathode voltage reduces.Therefore, during voltage in anode voltage reaches a certain scope that is higher than 3.6V (oxidized at this copper coil as anode collector), the problem of copper ion dissolving can take place under the situation of bag shape battery.Thereby battery is destroyed, makes that the charge/discharge cycle of battery is hindered after the overdischarge.In addition, when the active material of cathode content of additive was higher than 10 weight portions, cathode voltage descended fast during over-discharge test, thereby battery can show good effect in over-discharge test.But, at cathode surface the electrolyte reduction can take place, and battery capacity can be lowered.Therefore, in order to solve the problem that all exists in negative electrode and the anode, when integral battery door voltage became 0V, cathode potential was preferably 2V～3.6V, and anode potential is preferably 3.6V or lower.
Carry out over-discharge test as follows: under 300mA, be discharged to 3.0V, under 3mA, be discharged to 2.7V and under 1mA, be discharged to 0V.
Be used for active material of cathode of the present invention and can be any conventional active material of cathode, still, it preferably uses lithium transition-metal oxide.For example can use and be selected from LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2O
4, Li (Ni
aCo
bMn
c) O
2(its as, in 0＜a＜1,0＜b＜1,0＜c＜1, and a+b+c=1), LiNi
1-dCo
dO
2, LiCo
1-dMn
dO
2, LiNi
1-dMn
dO
2(wherein 0≤d＜1), Li (Ni
xCo
yMn
z) O
4(wherein 0＜x＜2,0＜y＜2,0＜z＜2, and x+y+z=2), LiMn
2-nNi
nO
4, LiMn
2-nCo
nO
4(wherein 0＜n＜2), LiCoPO
4, LiFePO
4Deng, preferably use LiCoO
2
Can use graphite, carbon, lithium metal and the alloy etc. of energy embedding/lithium ionic insertion/deinsertion for active material of positive electrode.The preferred Delanium that uses.Anode can comprise adhesive, and described adhesive is preferably PVDF (polyvinylidene fluoride) or SBR (styrene butadiene ribber).
For slider, preferably use the porous slider.For example, can use polytrimethylene-, poly-ethylidene-or the porous slider of polyolefin-Ji, but be not limited thereto.
Being used for electrolyte of the present invention is nonaqueous electrolyte, can comprise cyclic carbonate and linear carbonates.The example of cyclic carbonate comprises ethylene carbonate (EC), propylene carbonate (PC) and gamma-butyrolacton (GBL).The preferred example of linear carbonates comprises at least a carbonic ester that is selected from diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and carbonic acid first propyl ester (MPC).
In addition, except carbonate products, be used for electrolyte of the present invention and comprise lithium salts.More specifically, affiliated lithium salts is preferably selected from LiClO
4, LiCF
3SO
3, LiPF
6, LiBF
4, LiAsF
6And LiN (CF
3SO
2)
2
Lithium secondary battery of the present invention prepares by conventional method, promptly by insertion porous slider between negative electrode and anode, and introduces electrolyte.
Preferably, lithium secondary battery of the present invention is cylindrical battery, prismatic battery or bag shape battery.
Advanced effect
As mentioned before, according to the present invention the compound of general formula 1 expression is added in the negative electrode as the cathode active material feed additives, to improve over-discharge property.The additive that is used for active material of cathode can provide the lithium ion of such amount at least, with the irreversible capacity of compensation anode.Thereby anode voltage increases in the time of can preventing overdischarge by the irreversibility that increases negative electrode, so that cathode voltage descends fast, thereby battery capacity can recover 90% or higher after the overdischarge.
In addition, according to the active material of cathode that is used for lithium secondary battery, it comprise general formula 1 expression and wherein nickel partly replaced the lithium nickel oxide of (prerequisite is that y is not 0) by other element, or general formula 1 expression and lithium nickel oxide that applied by the oxide surface beyond the lithium nickel oxide is as the cathode active material feed additives, battery capacity does not significantly reduce after overdischarge, has kept the overall performance of battery simultaneously.In addition, can obtain good capacity restoration performance, and can prevent that battery from high temperature expanding.
Description of drawings
Fig. 1 represents to use the cathode potential and the anode potential of cathode active material feed additives of the present invention front and back.
Fig. 2 represents that the binary battery that is obtained by Comparative Examples 1 carries out the result of three utmost point bars test.
Fig. 3 represents that the binary battery that is obtained by the embodiment of the invention 1 carries out the result of three utmost point bars test.
Fig. 4 represents that the binary battery that is obtained by the embodiment of the invention 2 carries out the result of three utmost point bars test.
Fig. 5 represents that the binary battery that is obtained by the embodiment of the invention 3 carries out the result of three utmost point bars test.
Fig. 6 represents the x-ray diffraction pattern that is used for the cathode active material feed additives by embodiment 4 described method preparations.
Fig. 7 represents the x-ray diffraction pattern that is used for the cathode active material feed additives by embodiment 5 described method preparations.
Fig. 8 represents the x-ray diffraction pattern that is used for the cathode active material feed additives by embodiment 6 described method preparations.
Fig. 9 represents the x-ray diffraction pattern that is used for the cathode active material feed additives by embodiment 7 described method preparations.
Figure 10 represents the charge/discharge result by the battery of embodiment 4～7 described method preparations.
After Figure 11 represents that battery at high temperature stores, by the varied in thickness figure of the bag shape battery that is used for the cathode active material feed additives containing of embodiment 4～7 described method preparations.
Figure 12 represents to be used for by containing of embodiment 4,5 and 7 described method preparations the over-discharge test results of bag shape battery of cathode active material feed additives.
Figure 13 represents the over-discharge test results by the bag shape battery of comparative example 2 described method preparations.
Figure 14 and 15 represents SEM that is used for the cathode active material feed additives (ESEM micrograph) and EDS (energy-dispersive X-ray analysis instrument) analysis result by embodiment 8 described method preparations respectively.
Figure 16 and 17 represents SEM that is used for the cathode active material feed additives and the EDS analysis result by embodiment 11 described method preparations respectively.
Figure 18 and 19 represents SEM that is used for the cathode active material feed additives and the EDS analysis result by embodiment 12 described method preparations respectively.
Figure 20 represents the charging by the battery of embodiment 8～12 described method preparations.
After Figure 21 represents that battery at high temperature stores, by the varied in thickness of the bag shape battery that contains the cathode active material feed additives of the described methods preparation of embodiment 8～12.
Figure 22 represents the over-discharge test results by the bag shape battery of embodiment 8～12 described method preparations.
Figure 23 represents to be used for the sectional view of the conventional bag shape battery of the following example and comparative example.Wherein number 1 and be bag, the 2nd, lid, the 3rd, negative electrode, the 4th, anode, the 5th, cathode current collector, the 6th, anode current current-collector, the 7th, slider, the 8th, lithium metal, the 9th, electrolyte.
Realize mode of the present invention
Below will introduce preferred implementation of the present invention in detail.Be to be understood that only purpose of the following examples for setting forth, rather than limitation of the present invention.
By conventional method preparation bag shape binary battery.LiCoO
2As active material of cathode, and add Li
2NiO
2As additive, its addition is 2 weight portions based on 100 weight portion active material of cathode.More specifically, the LiCoO that in as the NMP of solvent, adds 78.4wt.%
2, 1.6wt.% Li
2NiO
2, the KS-6 (transduction agent) of 10wt.% and 10wt.% PVDF (adhesive) to form the cathode mix slurry, slurry is coated on the Al current-collector obtains negative electrode then.In addition, use Delanium and copper respectively, use to contain 1M LiPF as active material of positive electrode and anode collector
6The EC/PC/DEC-based sols as electrolyte, to obtain battery by conventional method.
The method that repeats embodiment 1 prepares battery, except the Li as the cathode active material feed additives
2NiO
2Consumption be 5 weight portions based on 100 weight portion cathode active materials.
The method that repeats embodiment 1 prepares battery, except the Li as the cathode active material feed additives
2NiO
2Consumption be 9 weight portions based on 100 weight portion cathode active materials.
Comparative Examples 1
The method that repeats embodiment 1 prepares battery, except do not use cathode active material feed additives (Li in negative electrode
2NiO
2).
Test example 1
The binary battery that obtains in embodiment 1～3 and the Comparative Examples 1 is carried out the test of three utmost point bars.The result is shown in Fig. 2～5.Usually, when battery performance is estimated with capacity, use the notion of integral battery door voltage.Integral battery door voltage is defined as at battery has under the situation of a negative electrode and two electrodes of an anode difference between cathode voltage and the anode voltage.Three utmost point bar battery systems also comprise and insert the lithium metal of battery as reference electrode except negative electrode and anode.Using these class three utmost point bodies of rod is the performance of measuring actual battery negative electrode and anode when charge/discharge cycle, this is based on reference electrode (lithium metal), by measuring the electrical potential difference between reference electrode (lithium metal) and negative electrode respectively, and the electrical potential difference between reference electrode (lithium metal) and anode.
As shown in Figure 2, in over-discharge test, comparative example 1 shows platform (representing with circle), and wherein anode voltage increases the dissolving that copper ion takes place in the back.On the other hand, shown in Fig. 3～5, embodiment 1～3 does not all show the platform of corresponding copper ion dissolving.
Replace the lithium oxide of nickel to mix with suitable equal proportion as aluminium salt as nickel salt and aluminum oxide as lithium salts, nickel oxide, then under 600 ℃ with solid phase reaction, acquisition is as the Li of cathode active material feed additives
2Ni
0.97Al
0.03O
2The x-ray diffraction pattern of cathode active material feed additives as shown in Figure 6.
Then, the LiCoO that in as the NMP of solvent, adds 92.12wt.%
2, super-P (transduction agent) of cathode active material feed additives, 3wt.% of 1.88wt.% and 3wt.% PVDF (adhesive) with formation cathode mix slurry, slurries are coated on the Al current-collector obtain negative electrode then.In addition, use Delanium and copper respectively, contain 1M LiPF as active material of positive electrode and anode collector
6The EC/PC/DEC-based sols as electrolyte, obtain battery by conventional method.The charge/discharge capacity of battery as shown in figure 10.
In addition, under 0.2C with bag shape battery charge to 4.2V, heat and rose to 90 ℃ from room temperature in 1 hour, store 4 hours down at 90 ℃, cool off then and returned to room temperature in 1 hour.Simultaneously, measure the varied in thickness of battery.The result is shown in 11.The over-discharge test results of battery such as table 1 and shown in Figure 12.
Except using magnesium as the element that replaces nickel, the method that repeats embodiment 4 is with the Li of preparation as the cathode active material feed additives
2Ni
0.97Mg
0.03O
2The X-ray diffracting spectrum of cathode active material feed additives as shown in Figure 7.According to embodiment 4 in identical mode use the cathode active material feed additives to prepare battery.The charge/discharge capacity of battery as shown in figure 10.
According to the method identical, measure the varied in thickness that battery at high temperature stores back pkt. shape battery with embodiment 4.The result as shown in figure 11, the over-discharge test results of battery such as table 1 and shown in Figure 12.
Except using boron as the element that replaces nickel, the method that repeats embodiment 4 is with the Li of preparation as the cathode active material feed additives
2Ni
0.97B
0.03O
2The x-ray diffraction pattern of cathode active material feed additives as shown in Figure 8.According to the mode identical, use the cathode active material feed additives to prepare battery with embodiment 4.The charge/discharge capacity of battery as shown in figure 10.
Use the method identical with embodiment 4, the measurement battery at high temperature stores the varied in thickness of back pkt. shape battery.The result as shown in figure 11.In addition, the over-discharge test results of battery is as shown in table 1.
Mix lithium salts and nickel salt with suitable geometric ratio, and in electric furnace, one react, to obtain the cathode active material feed additives.The x-ray diffraction pattern of cathode active material feed additives as shown in Figure 9.According to the mode identical, use the cathode active material feed additives to prepare battery with embodiment 4.The charge/discharge capacity of described battery as shown in figure 10.
Use the mode identical with embodiment 4, the measurement battery at high temperature stores the varied in thickness of back pkt. shape battery.The result as shown in figure 11.In addition, the over-discharge test results of battery such as table 1 and shown in Figure 12.
Comparative example 2
Except not to active material of cathode adds the cathode active material feed additives, the method that repeats embodiment 4 prepares battery.The over-discharge test results of battery such as table 1 and shown in Figure 13.
Table 1
| Discharge capacity (0.2C)/mA before the overdischarge | Discharge capacity after the overdischarge (0.2C)/mA | Capacity restorability after the overdischarge (%) | |
| | 732 | 682 | 93.2％ |
| Comparative example 2 | 728 | 464 | 63.7 |
| Embodiment | |||
| 4 | 742 | 699 | 94.2 |
| Embodiment | |||
| 5 | 738 | 687 | 93.1 |
| Embodiment | |||
| 6 | 729 | 673 | 92.3％ |
As can be seen, the battery that is prepared by embodiment 4～7 all shows similar charge from table 1 and Figure 10 and 12.The capacity of various batteries even also not obviously decline after overdischarge, and various battery has good capacity restorability after overdischarge.In addition, as table 1 and shown in Figure 13, the battery that is obtained by Comparative Examples 2 (wherein not adding the cathode active material feed additives that improves over-discharge property according to the present invention) is compared with other battery has relatively poor over-discharge property.
But, as can be seen from Figure 11, using Li
2Ni
0.97Al
0.03O
2Among the embodiment 4 as the cathode active material feed additives that improves over-discharge property, cell thickness changes little.With used Li
2NiO
2Embodiment 7 as the cathode active material feed additives compares, and has used Li respectively
2Ni
0.97Mg
0.03O
2And Li
2Ni
0.97B
0.03O
2Change little as cell thickness among the embodiment 5 and 6 of cathode active material feed additives.This shows with embodiment 7 compares, and the cathode active material feed additives that is used for improving over-discharge property according to embodiment 4～6 various is preventing all have good effect aspect the battery expansion at high temperature.
With 3mol% based on Li
2NiO
2Aluminium isopropoxide be dissolved in the ethanol.In smelting furnace, react the Li that obtains down to wherein adding lithium salts and nickel salt in 600 ℃
2NiO
2To form slurry.Filter described slurry to obtain filtering the back product by vacuum filter, will filter afterwards product in baking oven in 80 ℃ of following intensive dryings to obtain end product.Analyze end product by SEM and EDS.The result is respectively shown in Figure 14 and 15.
Then, the LiCoO that in as the NMP of solvent, adds 90.24wt.%
2, super-P (transduction agent) of the above-mentioned end product as the cathode active material feed additives, 3wt.% of 1.88wt.% and 3wt.% PVDF (adhesive) with formation cathode mix slurry, slurries are coated on the Al current-collector to obtain negative electrode then.In addition, use Delanium and copper respectively, use to contain 1M LiPF as active material of positive electrode and anode collector
6The solution of EC/PC/DEC-base as electrolyte, obtain battery by conventional method.The charge/discharge capacity of described battery as shown in figure 20.
In addition, bag shape battery is charged to 4.2V under 0.2C, heat and rose to 90 ℃ from room temperature in 1 hour, store 4 hours down, cool off then and returned to room temperature in 1 hour at 90 ℃.At this moment, measure the varied in thickness of battery.The result as shown in figure 21.The over-discharge test results of battery such as table 2 and shown in Figure 22.
Except using the precipitation method rather than decompression method separate slurry from solvent, the method that repeats embodiment 8 obtains the cathode active material feed additives, to prepare battery.The charging of described battery as shown in figure 20.
Use the method identical, measure battery and at high temperature store the varied in thickness of battery afterwards with embodiment 8.The result as shown in figure 21.In addition, the over-discharge test results of battery such as table 2 and shown in Figure 22.
Except slurry is replaced with the vacuum filter filtration with vacuum drying apparatus is dry, repeat embodiment 8 to obtain cathode active material feed additives and preparation battery.The charging of described battery as shown in figure 20.
Use the method identical, measure battery and at high temperature store the varied in thickness of battery afterwards with embodiment 8.The result as shown in figure 21.In addition, the over-discharge test results of described battery such as table 2 and shown in Figure 22.
Embodiment 11
Except replacing the aluminium isopropoxide, repeat embodiment 8 to obtain the cathode active material feed additives with the propyl alcohol zirconium.Use SEM and EDS to analyze described additive.The result is respectively as Figure 16 and shown in Figure 17.Use described additive preparation battery in the mode identical with embodiment 8.The charging of battery as shown in figure 20.
Use the method identical, measure battery and at high temperature store the varied in thickness of battery afterwards with embodiment 8.The result as shown in figure 21.In addition, the over-discharge test results of battery such as table 2 and shown in Figure 22.
In electric smelter, under 600 ℃, make the reaction of lithium salts and nickel salt, to obtain Li
2NiO
2Analyze Li by SEM and EDS
2NiO
2The result is respectively as Figure 18 and shown in Figure 19.Except using Li
2NiO
2As outside the additive of active material of cathode, prepare battery according to the mode identical with embodiment 8.The charging of battery as shown in figure 20.
Use the method identical, measure battery and at high temperature store the varied in thickness of battery afterwards with embodiment 8.The result as shown in figure 21.In addition, the over-discharge test results of battery such as table 2 and shown in Figure 22.
[comparative example 3]
Except not using the cathode active material feed additives, prepare battery according to the mode identical with embodiment 8.Use the method identical, measure battery and at high temperature store the varied in thickness of battery afterwards with embodiment 8.The result as shown in figure 21.In addition, the over-discharge test results of battery such as table 2 and shown in Figure 13.
Table 2
| Discharge capacity (0.2C)/mA before the overdischarge | Discharge capacity after the overdischarge (0.2C)/mA | Capacity restorability after the overdischarge (%) | |
| | 734 | 712 | 97.0％ |
| Comparative example 3 | 728 | 464 | 63.7 |
| Embodiment | |||
| 8 | 729 | 715 | 98.1 |
| Embodiment | |||
| 9 | 717 | 704 | 98.2 |
| Embodiment | |||
| 10 | 728 | 702 | 96.4％ |
| Embodiment 11 | 715 | 685 | 95.8％ |
Shown in Figure 15,17 and 19, the active material of cathode additive that improves over-discharge property by being used for of obtaining of embodiment 8 and 11 comprises the lithium nickel oxide that is applied by the oxide surface beyond the lithium nickel oxide.But obviously as can be seen, described face coat does not change the structure of the various cathode active material feed additives that are used for improving over-discharge property from Figure 14,16 and 18.
In addition, shown in table 2 and Figure 20 and 22, the various batteries that embodiment 8～12 obtains have similar charge.The capacity of various batteries even also not significantly reduction after overdischarge, and various battery all has good capacity restorability after overdischarge.On the other hand, as table 2 and shown in Figure 13, the battery that comparative example 3 obtains (wherein not adding the cathode active material feed additives that is used for improving over-discharge property according to the present invention) is compared the over-discharge property that performance is gone on business with other battery.
But as can be seen from Figure 21, the cell thickness of embodiment 8 changes little.Compare with embodiment 2, the cell thickness of embodiment 9～11 changes littler.This shows with embodiment 12 compares, and the various cathode active material feed additives that are used for improving over-discharge property according to embodiment 8～11 are preventing to have good effect aspect the battery expansion at high temperature.
According to the most practicable preferred implementation the present invention is set forth, but be to be understood that the present invention should not be restricted to disclosed execution mode and accompanying drawing.On the contrary, the present invention is intended to cover the various modifications and variations in claims purport and the scope.
Claims (12)
- One kind in the overdischarge process when negative electrode and anode potential poor (voltage) are 0V, regulate the method for lithium secondary battery negative electrode final voltage, it comprises by add lithium nickel oxide in the active material of cathode that contains lithium transition-metal oxide that can embedding/lithium ionic insertion/deinsertion and forms negative electrode as additive, the irreversible capacity of described lithium nickel oxide in first time charge/discharge cycle is greater than the irreversible capacity of described lithium transition-metal oxideGeneral formula 1 expression that wherein said lithium nickel oxide is partly replaced by other element by following wherein nickel, condition is that y is not 0, general formula 1 expression that perhaps described lithium nickel oxide is applied by the oxide surface of following quilt except that described lithium nickel oxide,General formula 1Li 2+xNi 1-yM yO 2+aWherein, x is the number of satisfied-0.5≤x≤0.5, y is the number that satisfies 0≤y＜1, and a is the number that satisfies 0≤a＜0.3, and M is at least a element that is selected from P, B, C, Al, Sc, Sr, Ti, V, Zr, Mn, Fe, Co, Cu, Zn, Cr, Mg, Nb, Mo and Cd.
- 2. method as claimed in claim 1, the adding degree of wherein said additive provide the irreversible lithium ion that causes irreversible consumption lithium reacting dose in the anode with compensation for the first time between charge period owing to anode surface formation SEI film at least.
- 3. method as claimed in claim 1, wherein said oxide except that lithium nickel oxide are oxide or the composite oxides that are selected from least a element of Al, Mg, Si, P, C, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Zr and Nb.
- 4. active material of cathode that is used for lithium secondary battery, it comprise can embedding/lithium ionic insertion/deinsertion lithium transition-metal oxide, it also comprises the lithium nickel oxide that the wherein nickel of following general formula 1 expression is partly replaced by other element, prerequisite is that y is not 0, perhaps general formula 1 expression and by the lithium nickel oxide of the coating of the oxide surface except that lithium nickel oxide, as additive:General formula 1Li 2+xNi 1-yM yO 2+aWherein, x is the number of satisfied-0.5≤x≤0.5, y is the number that satisfies 0≤y＜1, and a is the number that satisfies 0≤a＜0.3, and M is at least a element that is selected from P, B, C, Al, Sc, Sr, Ti, V, Zr, Mn, Fe, Co, Cu, Zn, Cr, Mg, Nb, Mo and Cd.
- 5. active material of cathode as claimed in claim 4, wherein said oxide except that lithium nickel oxide are oxide or the composite oxides that are selected from least a element of Al, Mg, Si, P, C, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Zr and Nb.
- 6. active material of cathode as claimed in claim 4, the compound of wherein said general formula 1 expression belongs to space group Immm.
- 7. active material of cathode as claimed in claim 6, the compound of its formula of 1 expression forms four-coordination planar structure (Ni, M) O 4, and the shared face that forms by O-O of two four-coordination planar structures that face with each other, thereby form main chain.
- 8. active material of cathode as claimed in claim 6, the compound of its formula of 1 expression has following lattice constant: a=3.7+0.5 , b=2.8+0.5 , c=9.2+0.5 , α=90 ° wherein, β=90 ° and γ=90 °.
- 9. active material of cathode as claimed in claim 4, wherein lithium transition-metal oxide is to be selected from LiCoO 2, LiNiO 2, LiMnO 2, LiMn 2O 4, Li (Ni aCo bMn c) O 2, LiNi 1-dCo dO 2, LiCo 1-dMn dO 2, LiNi 1-dMn dO 2, Li (Ni xCo yMn z) O 4, LiMn 2-nNi nO 4, LiMn 2-nCo nO 4, LiCoPO 4And LiFePO 4At least a material, 0＜a＜1,0＜b＜1,0＜c＜1 wherein, a+b+c=1,0≤d＜1,0＜x＜2,0＜y＜2,0＜z＜2, x+y+z=2 and 0＜n＜2.
- 10. active material of cathode as claimed in claim 4, based on 100 weight portion active material of cathode, it comprises the cathode active material feed additives of 0.1-10 weight portion.
- 11. a lithium secondary battery comprises negative electrode, anode, slider and contains lithium salts and the nonaqueous electrolyte of electrolyte compound, wherein said negative electrode comprises as the active material of cathode of claim 4～10 in each.
- 12. as the lithium secondary battery of claim 11, wherein said lithium salts is selected from LiClO 4, LiCF 3SO 3, LiPF 6, LiBF 4, LiAsF 6And LiN (CF 3SO 2) 2At least a, described electrolyte compound is at least a carbonic ester that is selected from carbonic acid ethylidene ester (EC), propylene carbonate (PC), gamma-butyrolacton (GBL), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and carbonic acid first propyl ester (MPC).
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| CN111785958A (en) * | 2010-06-29 | 2020-10-16 | 尤米科尔公司 | High density and high voltage stable cathode material for secondary battery |
| CN110419131B (en) * | 2010-06-29 | 2020-08-11 | 尤米科尔公司 | High density and high voltage stable cathode material for secondary battery |
| KR101202334B1 (en) * | 2010-07-20 | 2012-11-16 | 삼성에스디아이 주식회사 | Positive electrode and Lithium battery comprising the same |
| DE102014220504A1 (en) * | 2014-10-09 | 2016-04-14 | Bayerische Motoren Werke Aktiengesellschaft | Additive for alkali metal-based, especially lithium-based energy storage |
| CN112242519B (en) * | 2019-07-17 | 2023-01-06 | 比亚迪股份有限公司 | Positive electrode material, preparation method thereof and solid-state lithium battery |
| CN114144911A (en) * | 2020-01-31 | 2022-03-04 | 株式会社Lg新能源 | Irreversible additive contained in positive electrode material for secondary battery, positive electrode material containing same, and secondary battery containing same |
| JP7282441B2 (en) * | 2020-07-28 | 2023-05-29 | エルジー エナジー ソリューション リミテッド | Irreversible additive contained in positive electrode material for secondary battery, positive electrode material containing same, and secondary battery containing positive electrode material |
| CN114725539A (en) * | 2021-02-10 | 2022-07-08 | 深圳市德方创域新能源科技有限公司 | Lithium supplement additive and preparation method thereof |
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