CN103253715A - Methods of producing cobalt hydroxide, cobalt oxide and lithium cobalt oxide - Google Patents
Methods of producing cobalt hydroxide, cobalt oxide and lithium cobalt oxide Download PDFInfo
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- CN103253715A CN103253715A CN2013100548897A CN201310054889A CN103253715A CN 103253715 A CN103253715 A CN 103253715A CN 2013100548897 A CN2013100548897 A CN 2013100548897A CN 201310054889 A CN201310054889 A CN 201310054889A CN 103253715 A CN103253715 A CN 103253715A
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Abstract
The invention provides methods of producing cobalt hydroxide, cobalt oxide and lithium cobalt oxide, aiming to obtain cobalt hydroxide and cobalt oxide with an average particle size of 5[mu]m, secondary particles of narrow particle size distribution and none particles of a particle size of less than 1[mu]m. The method of producing cobalt hydroxide is characterized by comprising the following neutralization process that a cobalt aqueous solution (solution A) and an aqueous alkali solution (solution B) are added into an aqueous solution (solution C) for neutralization reaction at a temperature of 55-85 DEG C, wherein the cobalt aqueous solution (solution A) is a cobalt aqueous solution having glycine, and the content of glycine is 0.010-0.300 mol relative to one mole of cobalt of atoms by conversion.
Description
Technical field
The present invention relates to cobaltous hydroxide or cobalt oxide, relate in particular to cobaltous hydroxide that the manufacturing raw material of suitable lithium cobalt composite oxide as secondary lithium batteries uses or the manufacture method of cobalt oxide.In addition, the present invention relates to the manufacture method of the cobalt acid lithium of secondary lithium batteries.
Background technology
In recent years, along with the portability of household electrical appliance, no electric wireization advance fast, as the power supply of miniaturized electronicss such as laptop personal computer, mobile phone, pick up camera, lithium-ion secondary cell is practical.For this lithium-ion secondary cell, since having reported cobalt acid lithium (LiCoO
2) can be used as since the positive active material of lithium-ion secondary cell, launch energetically about the research and development of lithium-transition metal composite oxide, numerous schemes have been proposed so far.
As lithium-transition metal composite oxide, preferably use cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2), lithium manganate (LiMn
2O
4) etc., LiCoO particularly
2Owing to aspects such as its security, charge/discharge capacity are widely used.
In recent years, because the demand of the high capacity of lithium secondary battery, but the composite oxides of the cobalt acid lithium class of the secondary lithium batteries of needs high capacity.
As the gimmick that is used for making the lithium secondary battery high capacity, carried out following method etc. so far: mix oarse-grained cobalt acid lithium (1) with short grained cobalt acid lithium, improve the filling ratio of positive active material, thereby the capacity that increases unit volume is realized high capacity (for example patent documentation 1); (2) with LiCoO
2Composition change to as LiNi
0.85Co
0.15O
2, increase the capacity of unit weight, thereby realize high capacity (for example patent documentation 2).
Yet there is following problems in the method for above-mentioned (1): small-particle can influence the security of battery, especially follows the reaction of itself and nonaqueous electrolytic solution and the gas that produces can become many when discharging and recharging repeatedly.In addition, there is following problems in the method for above-mentioned (2): because LiNi
0.85Co
0.15O
2Manufacturing in the lithium compound that uses can be residual and influence the security of battery as residual alkali, the reaction of following itself and nonaqueous electrolytic solution that especially when discharging and recharging repeatedly, takes place and the gas that produces can become many.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-182564 communique (claims)
Patent documentation 2: Japanese kokai publication hei 11-060243 communique (claims)
Summary of the invention
The problem that invention will solve
Therefore, need to replace the gimmick of above-mentioned existing method.As the method that makes the lithium secondary battery high capacity, can consider by increasing LiCoO
2Particle diameter improve tap density, improve the method for capacity of the battery of unit volume.
Known use median size is particularly also excellent in security as the lithium secondary battery of positive active material to 10 ~ 35 μ m, the size-grade distribution cobalt that also narrow and particulate composition is few acid lithium greatly.
This median size more greatly to the cobalt of 10 ~ 35 μ m acid lithium need use usually median size less than the fine tricobalt tetroxide of 5 μ m as the cobalt source, make lithium compound nearly more than 1.03 by the molar ratio computing of Li/Co, react and make particle growth.Yet the Quilonum Retard of excessive part can directly remain in the cobalt acid lithium, and the result can make the battery performance variation on the contrary, also can occur the problem of battery security owing to gas generation etc.
Can think, if will increase to more than the 5 μ m as the cobaltous hydroxide of making the raw material use or the particle diameter of cobalt oxide, then can be as far as possible with controlling lowlyer with the overrate of the lithium compound of cobaltous hydroxide or cobalt oxide reaction, can obtain the cobalt acid lithium of median size 10 ~ 35 μ m.
In addition, the size-grade distribution of considering cobalt acid lithium depends on as the cobalt oxide in cobalt source, the size-grade distribution of cobaltous hydroxide, and therefore to develop narrow particle size distribution, median size be that 5 μ m are above and do not contain cobaltous hydroxide and the cobalt oxide of the following particulate composition of particle diameter 1 μ m in fact in expectation.
Therefore, the objective of the invention is to obtain that median size is that 5 μ m are above, the narrow particle size distribution of second particle, do not contain cobaltous hydroxide and the cobalt oxide of the following particulate composition of particle diameter 1 μ m in fact.Even if the present invention also aims to obtain median size does not contain the particulate composition below the particle diameter 1 μ m greatly less and in fact yet to the residual alkali number of 10 ~ 35 μ m cobalt acid lithium.
For the scheme of dealing with problems
The inventor etc. further investigate repeatedly in view of above-mentioned practical situation, found that, in the neutralization reaction that is dissolved with the cobalt aqueous solution of cobalt salt (A liquid) and alkali aqueous solution (B liquid), if use and have the cobalt aqueous solution of glycine as the cobalt aqueous solution (A liquid), make the mol ratio of cobalt in the cobalt aqueous solution (A liquid) and glycine in specific scope, and A liquid and B liquid added in the water (C liquid) that does not contain glycine carry out neutralization reaction, then can obtain for the median size of primary particle after assembling be second particle more than the 5 μ m, the narrow particle size distribution of second particle, do not contain the cobaltous hydroxide of the following particulate composition of particle diameter 1 μ m in fact, thereby finished the present invention.
Namely, the present invention (1) provides a kind of manufacture method of cobaltous hydroxide, it is characterized in that, this method have following in and operation: the cobalt aqueous solution (A liquid) and alkali aqueous solution (B liquid) added in the water solvent (C liquid) carry out neutralization reaction, thereby obtain cobaltous hydroxide, wherein, the cobalt aqueous solution (A liquid) is the cobalt aqueous solution that contains glycine, with respect to 1 mole of cobalt of pressing the atom conversion, the content of glycine is 0.010 ~ 0.300 mole.
In addition, the present invention (2) provides a kind of manufacture method of cobalt oxide, it is characterized in that this method has following oxidizing roasting operation: under 200 ~ 700 ℃ to the manufacture method of the cobaltous hydroxide that carries out the present invention (1) and the cobaltous hydroxide that obtains carries out roasting makes its oxidation, thereby obtain cobalt oxide.
In addition, the present invention (3) provides the manufacture method of a kind of cobalt acid lithium, it is characterized in that this method has following operation: the particle mixed processes, will carry out the present invention (1) cobaltous hydroxide manufacture method and the cobaltous hydroxide that obtains mixes with lithium compound; The roasting reaction process, the granular mixture that obtains carrying out this particle mixed processes carries out roasting.
In addition, the present invention (4) provides the manufacture method of a kind of cobalt acid lithium, it is characterized in that this method has following operation: the particle mixed processes, will carry out the present invention (2) cobalt oxide manufacture method and the cobalt oxide that obtains mixes with lithium compound; The roasting reaction process, the granular mixture that obtains carrying out this particle mixed processes carries out roasting.
The effect of invention
According to the present invention, can provide that median size is that 5 μ m are above, the narrow particle size distribution of second particle, not contain cobaltous hydroxide and the cobalt oxide of the following particulate composition of particle diameter 1 μ m in fact.In addition, according to the present invention, even can obtain median size greatly to the residual alkali number of 10 ~ 35 μ m also less, do not contain the cobalt acid lithium of the particulate composition below the particle diameter 1 μ m in fact.
In addition, the cobalt oxide that obtains of the cobaltous hydroxide that will obtain with the manufacture method of carrying out cobaltous hydroxide of the present invention or the manufacture method of carrying out cobalt oxide of the present invention be the cobalt acid lithium of cobalt source manufacturing as the capacity height of the unit volume of the lithium secondary battery of positive active material, cycle characteristics also excellent, security is also excellent.
Description of drawings
Fig. 1 is the particle size distribution figure of the cobaltous hydroxide that obtains among the embodiment 1.
Fig. 2 is the particle size distribution figure of the cobaltous hydroxide that obtains among the embodiment 2.
Fig. 3 is the particle size distribution figure of the cobaltous hydroxide that obtains in the comparative example 1.
Fig. 4 is the particle size distribution figure of the cobaltous hydroxide that obtains in the comparative example 2.
Fig. 5 is the particle size distribution figure of the cobaltous hydroxide that obtains in the comparative example 3.
Fig. 6 is the particle size distribution figure of the cobalt acid lithium that obtains among the embodiment 5.
Fig. 7 is the particle size distribution figure of the cobalt acid lithium that obtains in the comparative example 6.
Embodiment
The manufacture method of cobaltous hydroxide of the present invention is characterised in that, this method have following in and operation: the cobalt aqueous solution (A liquid) and alkali aqueous solution (B liquid) added in the water solvent (C liquid) carry out neutralization reaction, thereby obtain cobaltous hydroxide, wherein, the cobalt aqueous solution (A liquid) is the cobalt aqueous solution that contains glycine, with respect to 1 mole of cobalt of pressing the atom conversion, the content of glycine is 0.010 ~ 0.300 mole.
In the manufacture method of cobaltous hydroxide of the present invention and operation be by A liquid and B liquid are added to the operation that the cobalt salt that makes in the C liquid in the A liquid and the alkali in the B liquid react in C liquid.
A liquid is to contain glycine (NH
2CH
2COOH) the cobalt aqueous solution.And A liquid is by with glycine with cobalt salt is soluble in water prepares.
Cobalt salt as in the A liquid is not particularly limited, and can list the muriate, nitrate, vitriol of cobalt etc., in the middle of these, preferably can not sneak into the vitriol of impurity because of chlorine.In addition, can make a spot of other metal-salt coexistences as required.As the metal-salt that can coexist, for example can list the metal-salt of nickel, manganese, magnesium, aluminium, titanium etc.
Concentration to the cobalt ion in the A liquid is not particularly limited, and presses atom and converts, and is preferably 1.0 ~ 2.2 moles/L, is preferably 1.5 ~ 2.0 moles/L especially.By making concentration of cobalt ions in the A liquid in above-mentioned scope, productivity can become well, and is not easy to take place cobalt salt and separates out from A liquid.On the other hand, if the concentration of cobalt ions in the A liquid less than above-mentioned scope, then productivity reduces easily, in addition, if surpass above-mentioned scope, then cobalt salt is separated out from A liquid easily.
For the content of the glycine in the A liquid with respect to cobalt, be 0.010 ~ 0.300 mole with respect to 1 mole of cobalt that converts by atom, be preferably 0.050 ~ 0.200 mole, be preferably 0.050 ~ 0.180 mole especially.By make glycine in the A liquid with respect to the content of cobalt in above-mentioned scope, can make the size distribution narrow of the second particle of cobaltous hydroxide.On the other hand, if the glycine in the A liquid with respect to the content of cobalt less than above-mentioned scope, then the size-grade distribution of the second particle of cobaltous hydroxide broadens, in addition, if surpass above-mentioned scope, then a part of unreacted cobalt salt can remain in the reaction solution, causes the productivity variation.
B liquid is alkali aqueous solution.And B liquid is by preparing alkali is water-soluble.
Alkali as in the B liquid is not particularly limited, and can list alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide etc., in the middle of these, sets out aspect industrial cheapness, preferred sodium hydroxide.
The concentration of B liquid is suitably selected according to concentration and the total amount of the cobalt ion in the A liquid with the total amount of adding the alkali in the C liquid to.
The concentration of B liquid is preferably 5 ~ 15 moles/L, is preferably 5 ~ 10 moles/L especially.
The C liquid that is used for interpolation A liquid and B liquid is the water that does not contain glycine.Need to prove, though C liquid does not contain glycine, can contain for example pH regulator agent as required.
For the addition of the A liquid that adds in C liquid and B liquid, the total mole number of the hydroxide ion in the B liquid is preferably 1.8 ~ 2.1, is preferably 1.9 ~ 2.0 amount especially with respect to the ratio (the total Co ion in the mole number of the total OH ion in the B liquid/A liquid is by the mole number of atom conversion) of the total mole number of the cobalt ion that converts by atom in the A liquid.Total mole number by making the hydroxide ion in the B liquid in above-mentioned scope, can obtain the cobaltous hydroxide of target and the cobalt ion of remained unreacted in reaction solution (C liquid) not with respect to the ratio of the total mole number of the cobalt ion that converts by atom in the A liquid easily.
Then, in and in the operation, be selected in advance in the reaction vessel and add C liquid, in this C liquid, add A liquid and B liquid.Lofting amount before the reaction of C liquid namely adds the amount of the C liquid before A liquid and the B liquid and waits suitably according to the whipped state of the C liquid in the capacity of the cobalt amount in the A liquid, reaction vessel, the reaction vessel and select.
In and operation in, the temperature of reaction of neutralization reaction is 55 ~ 85 ℃, is preferably 60 ~ 75 ℃, is preferably 65 ~ 75 ℃ especially.That is, in and in the operation, the temperature of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid, namely the temperature of the C liquid before the reaction and the temperature of the reaction solution in the neutralization reaction (C liquid) they are 55 ~ 85 ℃, are preferably 60 ~ 75 ℃, are preferably 65 ~ 75 ℃ especially.The temperature of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid by making in above-mentioned scope, the tendency that exists the content of the particulate composition that median size increases, particle diameter 1 μ m is following of the second particle of cobaltous hydroxide to reduce.On the other hand, if the temperature of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid less than above-mentioned scope, the tendency that the particulate composition of then exist the median size of the second particle of cobaltous hydroxide to reduce, particle diameter 1 μ m is following increases.In addition, the temperature of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid surpasses above-mentioned scope, the tendency that the particulate composition of also can exist the median size of the second particle of cobaltous hydroxide to reduce, particle diameter 1 μ m is following increases.
In and in the operation, the pH of the C liquid before the pH of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid, the reaction and the pH of the reaction solution in the neutralization reaction (C liquid) are 9.0 ~ 11.0, are preferably 9.5 ~ 10.5, are preferably 9.8 ~ 10.2 especially.The pH of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid by making is in above-mentioned scope, can obtain the cobaltous hydroxide of the big and narrow particle size distribution of the median size of second particle.On the other hand, if the pH of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid is lower than above-mentioned scope, then a part of unreacted cobalt ion can remain in the reaction solution, causes productivity to reduce easily, in addition, the gained cobaltous hydroxide contains the salts such as sulfate radical as impurity easily.In addition, if the pH of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid is higher than above-mentioned scope, then the median size of the second particle of cobaltous hydroxide diminishes easily, produces molecule, causes size-grade distribution to broaden easily.Need to prove, in and in the operation, the pH of the reaction solution (C liquid) when adding to A liquid and B liquid in the C liquid can be by selecting hydroxide ion concentration, the concentration of hydroxide ion in the B liquid in the B liquid for example with respect to the ratio of the concentration of the cobalt ion in the A liquid, the B liquid phase is regulated for the conditions such as ratio of the interpolation speed of A liquid when adding to C liquid.
In and in the operation, the interpolation speed of the hydroxide ion in the B liquid when adding to A liquid and B liquid in the C liquid is preferably 1.8 ~ 2.1 with respect to the ratio (B liquid/A liquid) of the interpolation speed of the cobalt ion in the A liquid, is preferably 1.9 ~ 2.0 especially.Need to prove that the interpolation speed of the hydroxide ion in the B liquid refers to respect to the ratio of the interpolation speed of the cobalt ion in the A liquid: the interpolation speed (moles/min) of the hydroxide ion in the B liquid that adds to reaction vessel is with respect to the ratio of the interpolation speed (moles/min) of the cobalt ion in the A liquid that adds to reaction vessel.
In and operation in, when adding to A liquid and B liquid in the C liquid, to being not particularly limited from beginning A liquid and B liquid added to the C liquid to adding the interpolation time that finishes, from industrial favourable angle, be preferably 0.5 ~ 10 hour, be preferably 1 ~ 5 hour especially.
In and operation in, the stirring velocity of the stirring velocity of the reaction solution (C liquid) when A liquid is mixed with B liquid, the C liquid before will reacting and the stirring velocity of the reaction solution in the neutralization reaction (C liquid), wait suitably according to the amount of the diameter of the size of reaction vessel, agitating vane, reaction solution and to select, the circumferential speed of preferred agitating vane is 0.5 ~ 4.0m/ second, and the circumferential speed of preferred especially agitating vane is 0.5 ~ 2.0m/ second.Then, in and operation in, aspect the median size increase of the second particle that makes cobaltous hydroxide easily, preferably, in the time period of A liquid and B liquid being added in the C liquid, with the time period of initial stage, preferably will set slowlyer from the stirring velocity that just begins to add to the time period after 1 hour.
In the manufacture method of cobaltous hydroxide of the present invention, by obtaining cobaltous hydroxide (second particle) with operation in so carrying out.
Carry out and operation after, by the cobaltous hydroxide (second particle) that generates in the reaction solution is carried out filtration under diminished pressure, centrifugation etc. and isolate the cobaltous hydroxide particle from reaction solution, wash as required, dry, broken.
About by the resulting cobaltous hydroxide of the manufacture method of carrying out cobaltous hydroxide of the present invention, it is that primary particle is assembled the second particle that forms, and median size is more than the 5 μ m, is preferably 8 ~ 40 μ m, its narrow particle size distribution.Need to prove that in the present invention, narrow particle size distribution represents that [median size (D50%)]/[standard deviation (SD value)] is 3.0 ~ 7.0, is preferably 3.5 ~ 6.5.
The cobaltous hydroxide that manufacture method by cobaltous hydroxide of the present invention is obtained, because the narrow particle size distribution of second particle, therefore be the material that the cobalt acid lithium that makes in the cobalt source also obtains narrow particle size distribution easily with this cobaltous hydroxide, by this cobalt acid lithium is used as positive active material for lithium secondary battery, is particularly conducive at the positive electrode material formation thickness of lithium secondary battery and films uniformly.
And then, the median size of the cobaltous hydroxide that the manufacture method by cobaltous hydroxide of the present invention obtains is more than the 5 μ m, be preferably 8 ~ 40 μ m, and there is not the following particulate composition of particle diameter 1 μ m in fact, therefore be the particulate composition that does not in fact also exist in the cobalt acid lithium made of cobalt source below the particle diameter 1 μ m with this cobaltous hydroxide, thereby by this cobalt acid lithium is used as cathode active material for lithium secondary battery, can guarantee the security of battery, the gas that especially can be suppressed at when discharging and recharging repeatedly following of taking place and the reaction of nonaqueous electrolytic solution produces.Need to prove that in the present invention, median size is the D50% in the volume distributed median that obtains with laser scattering method.In addition, in the present invention, do not contain the following particulate composition of particle diameter 1 μ m in fact and refer to: in the result who expresses with the volume distributed median that obtains with laser scattering method, the cumulative frequency of the particulate composition that particle diameter 1 μ m is following is below 1%, to be preferably below 0.1%.In addition, this also is same implication for cobalt oxide described later and cobalt acid lithium.
In addition, the maximum particle diameter of the cobaltous hydroxide that the manufacture method by cobaltous hydroxide of the present invention obtains is below the 100 μ m, by using the cobalt acid lithium that obtains as the cobalt source with this cobaltous hydroxide, can be not easy to take place so that mixing paste changes in time when making the positive plate of lithium secondary battery, problem such as peel off from aluminium foil easily.
Thus, according to the cobaltous hydroxide that obtains by the manufacture method of carrying out cobaltous hydroxide of the present invention, not only capacity height and the capacity sustainment rate height of unit volume can be provided, and security is also excellent, and then the also cobalt acid lithium used of excellent positive active material for lithium secondary battery of paint stability, operability.
The manufacture method of cobalt oxide of the present invention is characterised in that, this method has following oxidizing roasting operation: under 200 ~ 700 ℃ the cobaltous hydroxide that obtains by the manufacture method of carrying out cobaltous hydroxide of the present invention is carried out roasting and make its oxidation, thereby obtain cobalt oxide.
In the oxidizing roasting operation that the manufacture method of cobalt oxide of the present invention relates to, the maturing temperature during the roasting cobaltous hydroxide is 200 ~ 700 ℃, is preferably 300 ~ 500 ℃.In addition, roasting time is 2 ~ 20 hours, is preferably 2 ~ 10 hours.In addition, calcination atmosphere be in the air, the medium oxidizing atmosphere of oxygen.
Can be suitably to the cobalt oxide that obtains by the manufacture method of carrying out cobalt oxide of the present invention pulverize, classification.
Then, illustrate and use the cobaltous hydroxide that obtains by the manufacture method of carrying out cobaltous hydroxide of the present invention or the method for making cobalt acid lithium by the cobalt oxide that the manufacture method of carrying out cobalt oxide of the present invention obtains.
The cobaltous hydroxide that use obtains by the manufacture method of carrying out cobaltous hydroxide of the present invention or have following operation by manufacture method cobalt oxide, cobalt acid lithium that the manufacture method of carrying out cobalt oxide of the present invention obtains: particle mixed processes, the cobaltous hydroxide that will obtain by the manufacture method of carrying out cobaltous hydroxide of the present invention or mix with lithium compound by the cobalt oxide that the manufacture method of carrying out cobalt oxide of the present invention obtains; The roasting reaction process carries out roasting to the granular mixture that obtains in the grain mixed processes under 800 ~ 1150 ℃, thereby obtains cobalt acid lithium.
The particle mixed processes is the cobaltous hydroxide that will obtain by the manufacture method of carrying out cobaltous hydroxide of the present invention or the operation of mixing with lithium compound by the cobalt oxide that the manufacture method of carrying out cobalt oxide of the present invention obtains.
The lithium compound that relates to as the particle mixed processes; usually; just be not particularly limited so long as can be used as the material of raw material of the manufacturing usefulness of cobalt acid lithium; can list oxide compound, oxyhydroxide, carbonate, nitrate and the organic acid salt etc. of lithium; in the middle of these; consider preferred Quilonum Retard from the aspect of industrial cheapness.
Because reactive good, the median size of preferred lithium compound is 0.1 ~ 200 μ m, is preferably 2 ~ 50 μ m.
In the particle mixed processes; the cobaltous hydroxide that will obtain by the manufacture method of carrying out cobaltous hydroxide of the present invention or when mixing with lithium compound by the cobalt oxide that the manufacture method of carrying out cobalt oxide of the present invention obtains; the mole number of the lithium that converts by atom is 0.900 ~ 1.040 with respect to the ratio (mixing mol ratio, Li/Co) of the mole number of the cobalt that converts by atom; be preferably 0.950 ~ 1.030, be preferably 0.980 ~ 1.020 especially.Mole number by making the lithium that converts by atom in above-mentioned scope, is that the capacity sustainment rate of the lithium secondary battery of positive active material improve with cobalt acid lithium with respect to the ratio of the mole number of the cobalt that converts by atom.On the other hand, if the mole number of pressing the lithium that atom converts with respect to the mole number of the cobalt of press the atom conversion ratio less than above-mentioned scope, lithium deficiency then, thereby there is a unreacted cobalt, cause the loading capacity of unit weight that the tendency of remarkable minimizing is arranged thus, in addition, if surpass above-mentioned scope, then be the capacity sustainment rate reduction of the lithium secondary battery of positive active material with cobalt acid lithium.
In the particle mixed processes; as the cobaltous hydroxide that will obtain by the manufacture method of carrying out cobaltous hydroxide of the present invention or the method for mixing with lithium compound by the cobalt oxide that the manufacture method of carrying out cobalt oxide of the present invention obtains, for example can list ribbon mixer, Henschel mixer, high-speed mixer, nauta mixer (Nauta mixer) etc.
The roasting reaction process is: the cobalt oxide that obtains to the cobaltous hydroxide that obtains in the particle mixed processes, obtain by the manufacture method of carrying out cobaltous hydroxide of the present invention or by the manufacture method of carrying out cobalt oxide of the present invention and the granular mixture of lithium compound heat; thereby make the reaction of cobaltous hydroxide or cobalt oxide and lithium compound, obtain the operation of cobalt acid lithium.
In the roasting reaction process; when the granular mixture of the cobalt oxide that makes the cobaltous hydroxide that obtains by the manufacture method of carrying out cobaltous hydroxide of the present invention or obtain by the manufacture method of carrying out cobalt oxide of the present invention and lithium compound carries out the roasting reaction; the roasting temperature of reaction is 800 ~ 1150 ℃, is preferably 900 ~ 1100 ℃.In addition, the roasting reaction times is 1 ~ 30 hour, is preferably 5 ~ 20 hours.In addition, the roasting reaction atmosphere be in the air, the medium oxidizing atmosphere of oxygen.
Carry out after the roasting reaction process, as required the cobalt acid lithium that generates is carried out fragmentation or classification, obtain cobalt acid lithium.
The cobalt acid lithium that use obtains by the resulting cobaltous hydroxide of the manufacture method of carrying out cobaltous hydroxide of the present invention or by the resulting cobalt oxide of the manufacture method of carrying out cobalt oxide of the present invention forms the particle of narrow particle size distribution easily, by this cobalt acid lithium is used as cathode active material for lithium secondary battery, is particularly conducive at the positive electrode material formation thickness of lithium secondary battery and films uniformly.
And then, even use is 10 ~ 35 μ m by the resulting cobaltous hydroxide of the manufacture method of carrying out cobaltous hydroxide of the present invention or by the cobalt acid lithium median size that the resulting cobalt oxide of the manufacture method of carrying out cobalt oxide of the present invention obtains, residual Quilonum Retard is also few, and do not contain the following particulate composition of particle diameter 1 μ m in fact, therefore by this cobalt acid lithium is used as cathode active material for lithium secondary battery, not only the capacity height of unit volume and capacity sustainment rate height, and can guarantee the security of battery, the gas that especially can be suppressed at following of taking place when discharging and recharging repeatedly and the reaction of nonaqueous electrolytic solution produces.
Embodiment
Describe the present invention by the following examples in detail, but the present invention is not limited to these embodiment.
The preparation of the aqueous solution of raw material of reaction usefulness
(1) the cobalt aqueous solution 1
Rose vitriol 7 hydrates and 7.1g glycine that 425.5g is industrial are water-soluble, further add water so that total amount is 1L, the preparation cobalt aqueous solution 1.At this moment, the concentration of cobalt ions in the cobalt aqueous solution 1 converts by atom and counts 1.5 moles/L, and glycine concentration is 0.094 mole/L, and with respect to 1 mole of cobalt of pressing the atom conversion, glycine is 0.062 mole.
(2) the cobalt aqueous solution 2
Rose vitriol 7 hydrates that 425.5g is industrial are water-soluble, further add water so that total amount is 1L, the preparation cobalt aqueous solution 2.At this moment, the concentration of cobalt ions in the cobalt aqueous solution 2 converts by atom and counts 1.5 moles/L.
(3) the cobalt aqueous solution 3
Rose vitriol 7 hydrates that 425.5g is industrial are water-soluble, further add water so that total amount is 0.9L, the preparation cobalt aqueous solution 3.At this moment, the concentration of cobalt ions in the cobalt aqueous solution 3 converts by atom and counts 1.67 moles/L.
(4) alkali aqueous solution 1
Mode with the aqueous sodium hydroxide solution that forms 25 quality % is water-soluble with sodium hydroxide, the alkali aqueous solution 1 of preparation 0.5L.At this moment, the hydroxide ion concentration in the alkali aqueous solution 1 is 18.7 moles/L.
(5) initial setting-out liquid 1
With the water of 0.35L as initial setting-out liquid 1.That is, initial setting-out liquid 1 does not contain glycine.
(6) initial setting-out liquid 2
The 7.1g glycine is water-soluble, further add water so that total amount is 0.35L, prepare initial setting-out liquid 2.At this moment, the glycine concentration in the initial setting-out liquid 2 is 0.268 mole/L.
(7) initial setting-out liquid 3
The 1.4g glycine is water-soluble, further add water so that total amount is 0.35L, prepare initial setting-out liquid 3.At this moment, the glycine concentration in the initial setting-out liquid 3 is 0.053 mole/L.
(8) glycine solution 1
The 7.1g glycine is water-soluble, further add water so that total amount is 0.10L, preparation glycine solution 1.At this moment, the glycine concentration in the glycine solution 1 is 0.937 mole/L.
The manufacturing of cobaltous hydroxide
Add the initial setting-out liquid of 0.35L at the reaction vessel of 2L, be heated to the temperature of reaction shown in the table 1.
Then, stirring velocity by record in the table 1 stirs the reaction solution in the reaction vessel (initial setting-out liquid) on one side, on one side in reaction vessel, carry out following operation so that the pH of reaction solution reaches the mode of the pH of record in the table 1: embodiment 1 and 2 and comparative example 1 and 2 in, press the temperature of reaction shown in the table 1 and the dropping time dropping cobalt aqueous solution and alkali aqueous solution; In comparative example 3, press the temperature of reaction shown in the table 1 and the dropping time dropping cobalt aqueous solution, alkali aqueous solution and glycine solution, carry out neutralization reaction.
After the neutralization reaction, the cooling reaction solution then, filters and the washing product, and is dry under 70 ℃ then, obtains cobaltous hydroxide.
Each rerum natura of gained cobaltous hydroxide is shown in table 2.
Embodiment 3
The manufacturing of cobalt oxide
The cobaltous hydroxide that obtains among the embodiment 2 is carried out roasting in 2 hours in atmosphere, under 500 ℃, obtain cobalt oxide (Co
3O
4).
Each rerum natura of gained cobalt oxide is shown in table 2.
The manufacturing of cobalt acid lithium
The cobalt source of the above-mentioned cobaltous hydroxide that obtains, cobalt oxide and Quilonum Retard by the Li/Co mixed in molar ratio shown in the table 3, then, with the heating of the roasting temperature of reaction shown in the table 3, are made cobalt acid lithium.
Median size, tap density, capacity sustainment rate, initial discharge capacity (unit weight), initial discharge capacity (unit volume) and the average working voltage of gained cobalt acid lithium are shown in table 3.
Estimate
(1) size-grade distribution of cobaltous hydroxide or cobalt oxide
Measure the median size, maximum particle diameter, minimum grain size of second particle, the content of particulate composition below the particle diameter 1 μ m by the laser diffraction and scattering method.Measure the Microtrac HRA(X-100 that uses Nikkiso Company Limited to make).
Need to prove, as size-grade distribution whether the value of median size (the D50%)/standard deviation (SD value) of narrow index also obtain according to the measurement result of size-grade distribution.
In addition, the size-grade distribution of the cobaltous hydroxide that obtains in embodiment 1 and 2 is illustrated in Fig. 1 ~ Fig. 2, the particle size distribution figure of the cobaltous hydroxide that obtains in the comparative example 1 ~ 3 is shown in Fig. 3 ~ Fig. 5 respectively.In addition, the particle size distribution figure with the cobalt that obtains in embodiment 5 and the comparative example 6 acid lithium is shown in Fig. 6 ~ Fig. 7 respectively.
(2) tap density
According to the method for the apparent density of putting down in writing among the JIS-K-5101 or apparent specific volume, in the graduated cylinder of 50ml, put into the 30g sample, be contained in Yuasa Ionics Co., Ltd. on the DUAL AUTOTAP device of Zhi Zaoing, vibrate 500 times, read capacity, calculate apparent density, as tap density.
(3) residual Quilonum Retard amount
With the unit of the accurate weighing of 30g sample to 10mg, put into beaker.Measure the 100ml deionized water with graduated cylinder, join in the beaker, stirred 5 minutes with magnetic stirrer.After stirring end, use filter paper filtering suspension, filtrate is reclaimed.Get 60ml filtrate with the graduated cylinder branch, carry out titration with automatic titration device with the N/10 hydrochloric acid soln, read Li
2CO
3Neutralization reaction in second terminal point.With each measured value substitution following formula, obtain residual alkali number.
Residual alkali number={ N
HCl* f
HCl* (A/1000) * (M
Li2CO3/ B) * (C/D) }/2 * 100
N
HCl: the volumetric molar concentration of the hydrochloric acid soln that titration is used
f
HCl: the titre of the hydrochloric acid soln that titration is used
A: until the dripping quantity (ml) of the required hydrochloric acid soln of neutralization
M
Li2CO3: Li
2CO
3Molecular weight
B: used sample size (g)
C: the amount (ml) that extracts the used deionized water of excessive partial L i
The amount of the filtrate that D:1 titration is used (ml))
The following battery performance test that carries out.
The making of lithium secondary battery
The cobalt acid lithium, 6 weight % powdered graphites, the 3 weight % polyvinylidene difluoride (PVDF) that obtain in 91 weight % embodiment 4 ~ 5 and the comparative example 4 ~ 7 are mixed as anode mixture, it is dispersed in the mixing paste of preparation in the N-N-methyl-2-2-pyrrolidone N-.Dry after being coated on this mixing paste on the aluminium foil, as to suppress, be die-cut into diameter 15mm disk obtains positive plate.
Use each structure manufacture button type lithium secondary battery such as this positive plate, isolated body, negative pole, positive pole, collector plate, installation part, outside terminal, electrolytic solution.Wherein, negative pole uses metallic lithium foil, and electrolytic solution uses in the mixing liquid of 1:1 of the ethylene carbonate of 1L and Methyl ethyl carbonate and dissolved 1 mole of LiPF
6And the solution that obtains.
The performance evaluation of battery
The button type lithium secondary battery of made is at room temperature worked under following test conditions, following battery performance is estimated.
(1) test conditions of cycle characteristics evaluation
At first, charge to 4.4V with 0.5C with 2 hours, under 4.4V, carry out the constant-current constant-voltage charging (CCCV charging) of 3 hours sustaining voltages again.Then, carry out with 0.2C constant current discharge (CC discharge) to the discharging and recharging of 2.7V, with these operations as 1 circulation, each circulation mensuration loading capacity.Should circulate and repeat 20 times.
(2) initial discharge capacity (unit weight)
The loading capacity of the 1st circulation during cycle characteristics estimated is as initial discharge capacity.
(3) initial discharge capacity (unit volume)
The electrode density that records during by the making positive plate and the integrating of initial discharge capacity (unit weight) go out.
(4) capacity sustainment rate
According to the 1st circulation and the 20th the circulation loading capacity (unit weight) separately in the cycle characteristics evaluation, calculate the capacity sustainment rate by following formula.
Capacity sustainment rate (%)=(loading capacity of the loading capacity of the 20th circulation/1st circulation) * 100
(5) average working voltage
The average working voltage of the 20th circulation during cycle characteristics estimated is as average working voltage.
Table 1
1) stirs circumferential speed and mixing back 1 hour of beginning with 0.5m/ second, the speed with 2.0m/ second stirs afterwards for " 0.5 ~ 2.0 " refers to.
Table 2
Table 3
As shown in Table 3, to be that the median size that makes in the cobalt source is that the cobalt acid lithium of 10 ~ 35 μ m is as the lithium secondary battery of positive active material higher be the 450(mAh/mL of loading capacity of unit volume not only with cobaltous hydroxide of the present invention and cobalt oxide) more than, the capacity sustainment rate is also higher is more than 96%, and the following particulate composition of particle diameter 1 μ m and residual Quilonum Retard also control lessly, thereby battery security is also excellent.
Utilizability on the industry
According to the present invention, can obtain narrow particle size distribution, residual Quilonum Retard few, do not contain the cobalt acid lithium of median size 10 ~ 35 μ m of the particulate composition of particle diameter 1 μ m in fact, capacity height that therefore can manufacturer's volume and capacity sustainment rate height, security be excellent lithium secondary battery also.
Claims (5)
1. the manufacture method of a cobaltous hydroxide, it is characterized in that, this method have following in and operation: the cobalt aqueous solution (A liquid) and alkali aqueous solution (B liquid) added in the water solvent (C liquid) carry out neutralization reaction, thereby obtain cobaltous hydroxide, wherein, the cobalt aqueous solution (A liquid) is the cobalt aqueous solution that contains glycine, and with respect to 1 mole of cobalt of pressing the atom conversion, the content of glycine is 0.010 ~ 0.300 mole.
2. the manufacture method of cobaltous hydroxide according to claim 1 is characterized in that, in described and in the operation, time carries out neutralization reaction in pH9 ~ 11.
3. the manufacture method of a cobalt oxide, it is characterized in that, this method has following oxidizing roasting operation: under 200 ~ 700 ℃ to the manufacture method of carrying out each the described cobaltous hydroxide in claim 1 or 2 and the cobaltous hydroxide that obtains carries out roasting makes its oxidation, thereby obtain cobalt oxide.
4. the manufacture method of cobalt acid lithium is characterized in that this method has following operation: the particle mixed processes, will carry out the manufacture method of each the described cobaltous hydroxide in claim 1 or 2 and the cobaltous hydroxide that obtains mixes with lithium compound; The roasting reaction process, the granular mixture that obtains carrying out this particle mixed processes carries out roasting.
5. the manufacture method of cobalt acid lithium is characterized in that this method has following operation: the particle mixed processes, will carry out the manufacture method of the described cobalt oxide of claim 3 and the cobalt oxide that obtains mixes with lithium compound; The roasting reaction process, the granular mixture that obtains carrying out this particle mixed processes carries out roasting.
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| JP2012034821A JP5961004B2 (en) | 2012-02-21 | 2012-02-21 | Method for producing cobalt hydroxide, method for producing cobalt oxide, and method for producing lithium cobaltate |
| JP2012-034821 | 2012-02-21 |
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|---|---|---|---|---|
| CN105481025A (en) * | 2015-12-11 | 2016-04-13 | 郑州大学 | Porous cobalt hydroxide material, and preparation method and applications thereof |
| CN111498913A (en) * | 2020-05-12 | 2020-08-07 | 北京林业大学 | Preparation method and application of cobaltosic oxide nanoparticles |
| CN114790012A (en) * | 2022-04-22 | 2022-07-26 | 格林美（无锡）能源材料有限公司 | Lithium cobaltate positive electrode material and preparation method and application thereof |
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| KR102691440B1 (en) * | 2018-09-03 | 2024-08-01 | 주식회사 엘지에너지솔루션 | Positive electrode active material powder, method for manufacturing the same, lithium rechargeable battery including the same |
| CN114105216B (en) * | 2021-10-27 | 2024-03-29 | 厦门厦钨新能源材料股份有限公司 | Cobalt hydroxide with micro-crack structure, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1190947A (en) * | 1995-05-26 | 1998-08-19 | H·C·施塔克公司 | Spheroidally agglomerated basic cobalt (II) carbonate and spheroidally agglomerated cobalt (II) hydroxide, process for their production and their use |
| CN101113023A (en) * | 2006-07-26 | 2008-01-30 | 比亚迪股份有限公司 | Preparation method for secondary crystal lithium cobalt acid of positive electrode material of lithium ion cell |
| CN101585559A (en) * | 2009-06-14 | 2009-11-25 | 宁波科博特钴镍有限公司 | Preparation method of spherical cobaltosic oxide with high battery security |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848506A (en) * | 1994-08-05 | 1996-02-20 | Nikko Metal Pureeteingu Kk | Production of metal hydroxide powder |
| JP3609196B2 (en) * | 1996-04-01 | 2005-01-12 | 株式会社田中化学研究所 | Method for producing cobalt-nickel hydroxide for Li-ion secondary battery |
| JP3192374B2 (en) * | 1996-07-01 | 2001-07-23 | 正同化学工業株式会社 | Method for producing nickel hydroxide |
| JP3884796B2 (en) * | 1996-07-12 | 2007-02-21 | 日本化学工業株式会社 | Method for producing Ni-Co composite hydroxide |
| JPH11292547A (en) * | 1998-04-13 | 1999-10-26 | Ishihara Sangyo Kaisha Ltd | Lithium cobaltate, its production and lithium cell using that |
| FI110093B (en) * | 1999-06-29 | 2002-11-29 | Omg Kokkola Chemicals Oy | High volume, large particle size cobalt hydroxide or cobalt alloy hydroxide |
| JP4795753B2 (en) * | 2005-08-22 | 2011-10-19 | 大日精化工業株式会社 | Method for producing particulate cobalt trioxide pigment |
| CN101486494B (en) * | 2009-02-20 | 2010-09-08 | 武汉理工大学 | Method for synthesizing cobalt carbonate hydroxide nano material |
| JP5758743B2 (en) * | 2010-09-02 | 2015-08-05 | 日本化学工業株式会社 | Cobalt hydroxide and method for producing the same, and cobalt oxide and method for producing the same |
-
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- 2012-02-21 JP JP2012034821A patent/JP5961004B2/en active Active
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2013
- 2013-02-20 CN CN2013100548897A patent/CN103253715A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1190947A (en) * | 1995-05-26 | 1998-08-19 | H·C·施塔克公司 | Spheroidally agglomerated basic cobalt (II) carbonate and spheroidally agglomerated cobalt (II) hydroxide, process for their production and their use |
| CN101113023A (en) * | 2006-07-26 | 2008-01-30 | 比亚迪股份有限公司 | Preparation method for secondary crystal lithium cobalt acid of positive electrode material of lithium ion cell |
| CN101585559A (en) * | 2009-06-14 | 2009-11-25 | 宁波科博特钴镍有限公司 | Preparation method of spherical cobaltosic oxide with high battery security |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481025A (en) * | 2015-12-11 | 2016-04-13 | 郑州大学 | Porous cobalt hydroxide material, and preparation method and applications thereof |
| CN111498913A (en) * | 2020-05-12 | 2020-08-07 | 北京林业大学 | Preparation method and application of cobaltosic oxide nanoparticles |
| CN114790012A (en) * | 2022-04-22 | 2022-07-26 | 格林美（无锡）能源材料有限公司 | Lithium cobaltate positive electrode material and preparation method and application thereof |
| CN114790012B (en) * | 2022-04-22 | 2024-04-16 | 格林美（无锡）能源材料有限公司 | Lithium cobalt oxide positive electrode material and preparation method and application thereof |
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