CN102315427A - Cathode active substance for lithium ion secondary battery, preparation method and lithium ion secondary battery - Google Patents
Cathode active substance for lithium ion secondary battery, preparation method and lithium ion secondary battery Download PDFInfo
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Abstract
The invention provides a cathode active substance for lithium ion battery and a preparation method thereof. The method comprises the steps of 1) after titanium dioxide, chromic oxide, a lithium source and a solvent are mixed, conducting drying to remove the solvent to obtain first mixtures; 2) mixing the first mixtures obtained at the step 1 with the saturated solution of low-temperature fused salt and conducting drying to obtain second mixtures; and 3) calcining the second mixtures obtained at the step 2 and removing the low-temperature fused salt to obtain nanometer chromium lithium titanate, wherein the low-temperature fused salt is salt which can be fused under the condition of calcination and does not react with other components in the mixtures. The average grain size of the cathode active substance, i.e. the nanometer chromium lithium titanate prepared through the method provided by the invention is 200-250nm and the cathode active substance has an octahedral structure. The battery which is prepared by using the cathode active substance, i.e. the nanometer chromium lithium titanate provided by the invention has a good initial discharge specific capacity.
Description
Technical field
The invention relates to a kind of lithium ion secondary battery cathode active material and preparation method, and the lithium rechargeable battery that adopts this negative electrode active material.
Background technology
Along with fast development of information technology, various electronic products improve constantly the requirement of power supply.Lithium ion battery since energy density big, have extended cycle life, advantage such as memory-less effect, be the focus that people research and develop always.
Commercial lithium ion battery negative material adopts material with carbon element mostly; But negative pole carbon and organic electrolyte haptoreaction are carbon negative pole materials is causing one of key factor of battery capacity decay in the lithium battery commercial applications at present; Simultaneously in this process the volumetric expansion of negative material can take place, directly cause the decline of battery cycle life and cause that the material powder comes off from the copper collector.At present more novel " zero strain " material of lithium titanate of research can overcome the shortcoming of above-mentioned carbon negative pole to a certain extent, but its voltage platform higher (1.55V/Li), effects limit such as conductivity is lower its commercial application scope and progress.
Metatitanic acid chromium lithium becomes new research focus as a kind of novel negative material, and metatitanic acid chromium lithium material theoretical specific capacity is 157mAh/g, and reversible specific capacity can reach 150mAh/g.Not only solved material with carbon element haptoreaction and volumetric expansion problem, the voltage ratio lithium titanate material is low simultaneously, and the particularly important is its conductivity is 10 at normal temperatures
-4-10
-5S/cm is greatly improved with respect to lithium titanate material, and is high approximately 1000 times, and the next gap of low temperature is big (Solid State Ionics 117-1999265-271) more.
The preparation method of metatitanic acid chromium lithium generally has traditional high temperature solid-state method, sol-gal process etc., and the conventional high-temperature solid phase method is with TiO
2, Cr
2O
3With Li
2CO
3Perhaps LiOH etc. is synthetic under 900～1100 ℃ of high temperature, and the reaction time is generally 24h, and this method advantage is that technology is simple, and shortcoming is that the product particle is thicker, generally all is micron-sized, lack of homogeneity, and first discharge specific capacity is lower; Also have through Prepared by Sol Gel Method metatitanic acid chromium lithium in the prior art; It is raw material that this method generally adopts the organic alkoxide of titanium, lithium and the inorganic salts of chromium, prepares metatitanic acid chromium lithium through hydrolysis and sol gel process, and this method is compared with traditional high temperature solid-state method; The product chemical purity is high, good uniformity; But this method has adopted the organic compound cost too high, is complicated operation in addition, has limited it and has used widely; Adopt the battery of the prepared metatitanic acid chromium lithium of this method as negative electrode active material in addition, its first discharge specific capacity is lower.
Summary of the invention
The present invention is complicated for the preparation method who solves metatitanic acid chromium lithium in the prior art; The average grain diameter of prepared metatitanic acid chromium lithium is bigger; Adopt the less technical problem of first discharge specific capacity of the battery of metatitanic acid chromium lithium preparation, a kind of negative electrode active material that contains metatitanic acid chromium lithium and preparation method thereof is provided.
The present invention provides a kind of preparation method of nano barium titanate chromium lithium, and this method comprises:
1) with after titanium dioxide, chrome green, lithium source and the solvent, dry removing desolvated, and obtains first mixture;
2) first mixture that obtains in the step 1 is mixed with the saturated solution of low-temperature molten salt and drying, obtain second mixture;
3) with second mixture that obtains in the step 2, calcine and remove low-temperature molten salt, obtain nano barium titanate chromium lithium; Said low-temperature molten salt, for can fusion under the calcination condition and not with mixture in the salt of other composition reaction.
The present invention also provides a kind of negative electrode active material, and this active material contains nano barium titanate chromium lithium, and the average grain diameter of said nano barium titanate chromium lithium is 200-250nm, and this metatitanic acid chromium lithium is that the preparation method by metatitanic acid chromium lithium provided by the present invention prepares.
The present invention simultaneously also provides a kind of lithium rechargeable battery; Comprise battery container in this battery and be contained in electric core and the nonaqueous electrolytic solution in the battery container; Said electric core is stacked afterwards folding successively or is reeled by positive pole, barrier film, negative pole and forms, and contains negative electrode active material provided by the present invention in the said negative pole.
Preparation method's production technology of metatitanic acid chromium lithium material provided by the invention is simple; The average grain diameter of the metatitanic acid chromium lithium that makes according to the preparation method of metatitanic acid chromium lithium provided by the invention is 200-250nm; The particle of nano barium titanate chromium lithium is octahedral structure; The average grain diameter of the metatitanic acid chromium lithium of preparation method's preparation that the average grain diameter of the metatitanic acid chromium lithium that the present invention is prepared is provided in the prior art, and adopt the prepared nano barium titanate chromium lithium of the present invention to have higher first discharge specific capacity as the battery of negative material.
Description of drawings
Fig. 1 is the stereoscan photograph of the prepared nano barium titanate chromium lithium of the embodiment of the invention 1, and multiplication factor is 60.00K
Embodiment
Inventor of the present invention finds that through a large amount of experiments in the prior art, the preparation method of existing metatitanic acid chromium lithium comprises high temperature solid-state method, sol-gal process etc., and the conventional high-temperature solid phase method is with TiO
2, Cr
2O
3With Li
2CO
3Perhaps LiOH etc. is synthetic under 900～1100 ℃ of high temperature, and the reaction time is generally 24h, and this method advantage is that technology is simple, and shortcoming is that the product particle is thicker, generally all is micron-sized, lack of homogeneity; Also have through Prepared by Sol Gel Method metatitanic acid chromium lithium in the prior art, it is raw material that this method generally adopts the organic alkoxide of titanium, lithium and the inorganic salts of chromium, prepares metatitanic acid chromium lithium through hydrolysis and sol gel process; This method is compared with traditional high temperature solid-state method, and the product chemical purity is high, good uniformity, but this method has adopted the organic compound cost too high; Be complicated operation in addition; Limited it and used widely, in addition, the first discharge specific capacity of the battery of the metatitanic acid chromium lithium that the employing prior art for preparing is prepared is less; The inventor adopts method provided by the present invention can prepare a kind of nano barium titanate chromium lithium through discovering; This nano barium titanate chromium lithium has octahedral structure, adopts the lithium rechargeable battery of this nano barium titanate chromium lithium preparation to have higher first discharge specific capacity, and the inventor thinks to have special octahedral structure just because of the prepared metatitanic acid chromium lithium of the present invention; And the particle diameter of prepared metatitanic acid chromium lithium is less, can effectively improve the first discharge specific capacity of battery.
The present invention provides a kind of preparation method who contains the negative electrode active material of nano barium titanate chromium lithium, and this method comprises:
1) with after titanium dioxide, chrome green, lithium source and the solvent, dry removing desolvated, and obtains first mixture;
2) first mixture that obtains in the step 1 is mixed with the saturated solution of low-temperature molten salt and drying, obtain second mixture;
3) with second mixture that obtains in the step 2, calcine and remove low-temperature molten salt, wherein, said low-temperature molten salt be can fusion under the calcination condition and not with mixture in the salt that reacts of other composition.
Titanium dioxide, chrome green and lithium source mol ratio are 2: 1～2: 1.05 in step 1, and under preferable case, the mol ratio in titanium dioxide, chrome green and lithium source is 2: 1: 1.05.
With the method for titanium dioxide, chrome green, lithium source and solvent is conventional method, for example can use the method for stirring, ball milling to mix, and adopts the method for ball milling to mix among the present invention.
In step 1, disperse each other for better titanium dioxide, chrome green and lithium source; Can add proper amount of solvent; The solvent that is adopted among the present invention is an absolute ethyl alcohol, and the amount of absolute ethyl alcohol is unqualified, can titanium dioxide, chrome green and lithium source be uniformly dispersed to get final product.
Baking temperature in the step 1 is 80-100 ℃, and dry purpose is to remove the absolute ethyl alcohol that desolvates.
The source of lithium described in the step 1 can be the hydroxide of organic salt, inorganic salts or the lithium of lithium, and for example, the inorganic salts of said lithium can be lithium nitrate, lithium carbonate; The organic salt of said lithium can be lithium oxalate, lithium acetate; The hydroxide of said lithium can be lithium hydroxide, hydronium(ion) oxidation lithium.Under the preferable case, said lithium source can be in lithium carbonate, lithium hydroxide and the lithium nitrate one or more.
Low-temperature molten salt in the step 2 can for various can fusion under the calcination condition and not with mixture in the salt of other composition reaction, be selected from potassium chloride, potash, potassium sulfate, potassium nitrate, sodium chloride, sodium carbonate, sodium sulphate, the sodium nitrate one or more.
The hybrid mode of the saturated solution of first mixture and low-temperature molten salt is a hybrid mode known in the field in the step 2, such as mixing.
The weight ratio of first mixture and watery fusion salt is 1～3: 1～4 in the step 2.
The purpose of in step 2, selecting the low-temperature molten salt saturated solution for use is that other compositions in first mixture are mixed, and please explain principle wherein.In the preparation process; Diffusion velocity is in traditional solid phase environment in watery fusion salt for each material in first mixture, and effectively fast reaction speed shortens the reaction time; Reduce reaction temperature, and can make that each material mixes more even in the mixture of winning.
The temperature of the drying in the wherein said step 2 is 100 ℃.
Described in the step 3 calcining condition can for, reaction temperature is 500 ℃-700 ℃, the reaction time is 3-16 hour; Under the optimum condition, reaction temperature is 600 ℃, and the reaction time is 12 hours.
Said method of removing low-temperature molten salt is a conventional method, for conventionally known to one of skill in the art.For example can use water washing, the consumption of said water is enough to remove fully said low-temperature molten salt and gets final product.
The present invention provides a kind of lithium rechargeable battery; Comprise battery container in this battery and be contained in electric core and the nonaqueous electrolytic solution in the battery container; Said electric core is stacked afterwards folding successively or is reeled by positive pole, barrier film, negative pole and forms, and contains negative electrode active material provided by the invention in the said negative pole.Because inventive point of the present invention mainly is negative electrode active material and preparation thereof, so anodal preparation in the lithium rechargeable battery, the preparation of barrier film, the assembling of battery all adopt prepared in various methods known in the field, and this just repeats no more again.
Through concrete embodiment the present invention is done further explanation below.
Embodiment 1:
(1) nano barium titanate chromium lithium preparation
With TiO
2, Cr
2O
3And Li
2CO
3Place the ball grinder of 100ml by 2: 1: 1.05 proportionings, add the absolute ethyl alcohol of 80ml, ball milling 8h fully mixes.Drying is removed absolute ethyl alcohol, obtains first mixture, and it is in the saturated solution of solute that first mixture is dissolved in LiCl again; Wherein the weight ratio of first mixture and LiCl is 1: 3, and (ELE is prone to rein in electromechanics, is under the condition of 1100r/min at rotating speed EBF-22) at mixer; Stir 5min, fully mix, under 100 ℃ condition; Dry 24h obtains second mixture, and second mixture is heated to 600 ℃; Make the salt fusion, and after 12 hours, remove Li with the distilled water cyclic washing in this temperature insulation
+And Cl
-, the sample after the washing places 100 ℃ vacuum drying chamber dry, and dry 24h obtains nano barium titanate chromium lithium sample A1.With the pattern of JSM-5610LV type scanning electron microscopy (SEM) observation synthetic product, as shown in Figure 1, product is an octahedral structure; Average grain diameter is 210nm; And particle size is even, big or small basically identical, and the visible this method that adopts can be synthesized the excellent nano material of pattern.Adopt Japanese D/MAX-PC2200X x ray diffractometer x of science (Cu target, λ=0.15405nm) product is carried out the crystal structure analysis of thing phase.As shown in Figure 2, detect and be pure phase, each diffraction maximum and spinel-type LiCrTiO
4Standard card matches, and does not find other phases, shows that this material comprises purer spinelle LiCrTiO
4Phase, and peak shape is narrow and sharp, and promptly the sample crystalline form is better.
(2) preparation of pole piece
80 weight portion nano barium titanate chromium lithium materials, 10 weight portion adhesive polytetrafluoroethylene (PTFE)s, 10 weight portion conductive agent carbon blacks are joined in 110 parts by weight of deionized water, stir then and form cathode size stable, homogeneous.At 65 ℃ vacuum drying chamber inner dryings after 24 hours, take out, press down at the pressure of 4MPa that to process thickness be 0.03 millimeter, size is the pole piece of 15 millimeters of diameters.
(3) preparation of battery
With LiPF
6Be mixed with the solution that concentration is 1 mol with ethylene carbonate and dimethyl carbonate, obtain electrolyte.
Protect in argon gas atmosphere; Moisture is in the glove box below the 1ppm; With the above-mentioned pole piece that makes; Diameter be 15.8 millimeters, the metal lithium sheet of purity 99.9% as the Cellgard diaphragm paper composition battery battery core that to electrode and diameter is 16 millimeters, add 0.2 milliliter of electrolyte, process CR2016 type button cell T1.After assembling, shift out glove box, with electronic stamping machine pressurization.
(4) performance test
With battery ability meter (blue strange BK-6064A) test battery performance, the charging cut-ff voltage is 2.5 volts, and discharge cut-off voltage is 1.0 volts, and current density is 0.15 milliampere/centimetre
2, measure discharge capacity first, the discharge capacity first that usefulness obtains obtains first discharge specific capacity divided by the quality of metatitanic acid chromium lithium material, and the result is as shown in table 1.
Embodiment 2:
(1) nano barium titanate chromium lithium preparation
With TiO
2, Cr
2O
3And Li
2CO
3Place ball grinder by 2: 1: 1 proportionings, add simultaneously in the ball grinder of 100ml, the absolute ethyl alcohol that adds 80ml is a solvent, and ball milling 8h fully mixes, and dry removing desolvated, and obtains first mixture.It is in the saturated solution of solute that first mixture is dissolved with KCl; Wherein the weight ratio of first mixture and KCl is 1: 4, then under 100 ℃ condition, and dry 24h; Obtain second mixture; Second mixture is heated to 700 ℃ makes the KCl fusion, then 700 ℃ down insulation remove K with the distilled water cyclic washing after 12 hours
+And Cl
-, the sample after the washing places the dry 24h of 100 ℃ vacuum drying chamber, obtains nano barium titanate chromium lithium sample A2.Observe the pattern of synthetic product with JSM-5610LV type scanning electron microscopy (SEM); Product is an octahedral structure; Average grain diameter is 240nm; (display material is pure phase LiCrTiO for Cu target, λ=0.15405nm) product is carried out the crystal structure analysis of thing phase to adopt Japanese D/MAX-PC2200X x ray diffractometer x of science
4, do not contain solid phase impurity.
(2) preparation of pole piece
80 weight portion nano barium titanate chromium lithium composite material, 10 weight portion adhesive polytetrafluoroethylene (PTFE)s, 10 weight portion conductive agent carbon blacks are joined in 110 parts by weight of deionized water, stir then and form cathode size stable, homogeneous.At 65 ℃ vacuum drying chamber inner dryings after 24 hours, take out, press down at the pressure of 4MPa that to process thickness be 0.03 millimeter, size is the pole piece of 15 millimeters of diameters.
(3) preparation of battery
With LiPF
6Be mixed with the solution that concentration is 1 mol with ethylene carbonate and dimethyl carbonate, obtain electrolyte.
Protect in argon gas atmosphere; Moisture is in the glove box below the 1ppm; With the above-mentioned pole piece that makes; Diameter be 15.8 millimeters, the metal lithium sheet of purity 99.9% as the Cellgard diaphragm paper composition battery battery core that to electrode and diameter is 16 millimeters, add 0.2 milliliter of electrolyte, process CR2016 type button cell T2.After assembling, shift out glove box, with electronic stamping machine pressurization.
(4) performance test
With battery ability meter (blue strange BK-6064A) test battery performance, the charging cut-ff voltage is 2.5 volts, and discharge cut-off voltage is 1.0 volts, and current density is 0.15 milliampere/centimetre
2, measure discharge capacity first, the discharge capacity first that usefulness obtains obtains first discharge specific capacity divided by the quality of metatitanic acid chromium lithium material, and the result is as shown in table 1.
Embodiment 3:
(1) nano barium titanate chromium lithium preparation
With TiO
2, Cr
2O
3, LiNO
3By weight being the ball grinder that 2: 2: 1.05 proportionings place 100ml, add the 80ml absolute ethyl alcohol, ball milling 8h fully mixes.Dry removing desolvated, and it is in the saturated solution of solute that the gained mixture is dissolved in sodium carbonate again, and wherein the weight ratio of first mixture and sodium carbonate is 3: 3.5; Be heated to 100 ℃ and remove moisture; Be 24h heating time, obtains second mixture, second mixture is heated to 600 ℃ makes sodium carbonate fusion; And after being incubated 12 hours under 600 ℃, remove Na with the distilled water cyclic washing
+, the sample after the washing places 100 ℃ vacuum drying chamber dry, obtains sample A3; Adopt JSM-5610LV type scanning electron microscopy (SEM) to observe the pattern of A3, product is an octahedral structure, and average grain diameter is 245nm; Adopt Japanese D/MAX-PC2200X x ray diffractometer x (Cu target of science; λ=0.15405nm) product is carried out the crystal structure analysis of thing phase, shown in Fig. 4 c curve, obvious material is pure phase LiCrTiO among the figure
4, do not contain solid phase impurity.
(2) preparation of pole piece
Nano barium titanate chromium lithium material, 10 weight portion adhesive polytetrafluoroethylene (PTFE)s, the 10 weight portion conductive agent carbon blacks of 80 weight portions are joined in 110 parts by weight of deionized water, stir then and form cathode size stable, homogeneous.At 65 ℃ vacuum drying chamber inner dryings after 24 hours, take out, press down at the pressure of 4MPa that to process thickness be 0.03 millimeter, size is the pole piece of 15 millimeters of diameters.
(3) preparation of battery
With LiPF
6Be mixed with the solution that concentration is 1 mol with ethylene carbonate and dimethyl carbonate, obtain electrolyte.
Protect in argon gas atmosphere; Moisture is in the glove box below the 1ppm; With the above-mentioned pole piece that makes; Diameter be 15.8 millimeters, the metal lithium sheet of purity 99.9% as the Cellgard diaphragm paper composition battery battery core that to electrode and diameter is 16 millimeters, add 0.2 milliliter of electrolyte, process CR2016 type button cell T3.After assembling, shift out glove box, with electronic stamping machine pressurization.
(4) performance test
With battery ability meter (blue strange BK-6064A) test battery performance, the charging cut-ff voltage is 2.5 volts, and discharge cut-off voltage is 1.0 volts, and current density is 0.15 milliampere/centimetre
2, measure discharge capacity first, the discharge capacity first that usefulness obtains obtains first discharge specific capacity divided by the quality of metatitanic acid chromium lithium material, and the result is as shown in table 1.
Embodiment 4
(1) nano barium titanate chromium lithium preparation
With TiO
2, Cr
2O
3, LiOH places the ball grinder of 100ml by 2: 1.5: 1.05 proportionings, adds the absolute ethyl alcohol of 80ml, ball milling 8h fully mixes.Drying is removed absolute ethyl alcohol, obtains first mixture, and it is in the saturated solution of solute that first mixture is dissolved in sodium sulphate again; Wherein the weight ratio of first mixture and sodium sulphate is 3: 1, is heated to 100 ℃, and be 24h heating time; Obtain second mixture; Second mixture is heated to 700 ℃ makes the sodium sulphate fusion, then 700 ℃ down insulation remove Na with the distilled water cyclic washing after 12 hours
+And SO
4 -, the sample after the washing places 100 ℃ vacuum drying chamber dry, obtains sample A4.Adopt JSM-5610LV type scanning electron microscopy (SEM) to observe the pattern of A4; Observing A4 is octahedral structure; Average grain diameter is 230nm; (A4 is pure phase LiCrTiO for Cu target, λ=0.15405nm) A4 is carried out the crystal structure analysis of thing phase to adopt Japanese D/MAX-PC2200X x ray diffractometer x of science
4, do not contain solid phase impurity.
(2) preparation of pole piece
80 weight portion metatitanic acid chromium lithium materials, 10 weight portion adhesive polytetrafluoroethylene (PTFE)s, 10 weight portion conductive agent carbon blacks are joined in 110 parts by weight of deionized water, stir then and form cathode size stable, homogeneous.At 65 ℃ vacuum drying chamber inner dryings after 24 hours, take out, press down at the pressure of 4MPa that to process thickness be 0.03 millimeter, size is the pole piece of 15 millimeters of diameters.
(3) preparation of battery
With LiPF
6Be mixed with the solution that concentration is 1 mol with ethylene carbonate and dimethyl carbonate, obtain electrolyte.
Protect in argon gas atmosphere; Moisture is in the glove box below the 1ppm; With the above-mentioned pole piece that makes; Diameter be 15.8 millimeters, the metal lithium sheet of purity 99.9% as the Cellgard diaphragm paper composition battery battery core that to electrode and diameter is 16 millimeters, add 0.2 milliliter of electrolyte, process CR2016 type button cell T4.After assembling, shift out glove box, with electronic stamping machine pressurization.
(4) performance test
With battery ability meter (blue strange BK-6064A) test battery performance, the charging cut-ff voltage is 2.5 volts, and discharge cut-off voltage is 1.0 volts, and current density is 0.15 milliampere/centimetre
2, measure discharge capacity first, the discharge capacity first that usefulness obtains obtains first discharge specific capacity divided by the quality of metatitanic acid chromium lithium material, and the result is as shown in table 1.
Comparative Examples 1
(1) nano barium titanate chromium lithium preparation
Adopt LiOHH
2O, TiO
2And Cr
2O
3Be raw material, mixture ground in the aluminium oxide mortar with pestle in 2.05: 2: 1 in molar ratio, be pressed into bead (23mm diameter, 5mm thickness) again.Bead is calcined 20h in 800 ℃ of following air, obtain sample CT1.(CT1 is pure phase LiCrTiO for Cu target, λ=0.15405nm) CT1 is carried out the crystal structure analysis of thing phase to adopt Japanese D/MAX-PC2200X x ray diffractometer x of science
4, do not contain solid phase impurity.
(2) preparation of pole piece
80 weight portion metatitanic acid chromium lithium materials, 10 weight portion adhesive polytetrafluoroethylene (PTFE)s, 10 weight portion conductive agent carbon blacks are joined in 110 parts by weight of deionized water, stir then and form cathode size stable, homogeneous.At 65 ℃ vacuum drying chamber inner dryings after 24 hours, take out, press down at the pressure of 4MPa that to process thickness be 0.03 millimeter, size is the pole piece of 15 millimeters of diameters.
(3) preparation of battery
With LiPF
6Be mixed with the solution that concentration is 1 mol with ethylene carbonate and dimethyl carbonate, obtain electrolyte.
Protect in argon gas atmosphere; Moisture is in the glove box below the 1ppm; With the above-mentioned pole piece that makes; Diameter be 15.8 millimeters, the metal lithium sheet of purity 99.9% as the Cellgard diaphragm paper composition battery battery core that to electrode and diameter is 16 millimeters, add 0.2 milliliter of electrolyte, process CR2016 type button cell T4.After assembling, shift out glove box, with electronic stamping machine pressurization.
(4) performance test
With battery ability meter (blue strange BK-6064A) test battery performance, the charging cut-ff voltage is 2.5 volts, and discharge cut-off voltage is 1.0 volts, and current density is 0.15 milliampere/centimetre
2, measure discharge capacity first, the discharge capacity first that usefulness obtains obtains first discharge specific capacity divided by the quality of metatitanic acid chromium lithium material, and the result is as shown in table 1.
Table 1
From table 1, can find out; The first discharge specific capacity of battery provided by the present invention is all more than 150mAh/g; And the first discharge specific capacity of prepared sample CT1 is 143mAh/g in the Comparative Examples; First discharge specific capacity much smaller than the battery of the negative electrode active material that adopts the present invention's preparation; Simultaneously the average grain diameter of nano barium titanate chromium lithium provided by the present invention is much smaller than the average grain diameter of the sample that Comparative Examples provided, and therefore adopts method provided by the present invention can prepare the nano barium titanate chromium lithium of octahedral structure and the less nano barium titanate chromium lithium of average grain diameter; And employing contains the battery of the negative electrode active material of this kind nano barium titanate chromium lithium, has higher first discharge specific capacity.
Claims (10)
1. the preparation method of a lithium ion secondary battery cathode active material is characterized in that, this method comprises:
1) with after titanium dioxide, chrome green, lithium source and the solvent, dry removing desolvated, and obtains first mixture;
2) first mixture that obtains in the step 1 is mixed with the saturated solution of low-temperature molten salt and drying, obtain second mixture;
3) with second mixture that obtains in the step 2, calcine and remove low-temperature molten salt, obtain nano barium titanate chromium lithium; Said low-temperature molten salt, for can fusion under the calcination condition and not with mixture in the salt of other composition reaction.
2. the mol ratio in titanium dioxide, chrome green, lithium source is 2: 1～2: 1.05 among the preparation method of negative electrode active material according to claim 1, said step (1).
3. the preparation method of negative electrode active material according to claim 1, in the said step (2), the weight ratio of said first mixture and low-temperature molten salt is 1～3: 1～4.
4. the preparation method of negative electrode active material according to claim 1, in the said step (1), the lithium source is one or more in lithium carbonate, lithium hydroxide and the lithium nitrate.
5. the preparation method of negative electrode active material according to claim 1, in the said step (2), watery fusion salt is selected from one or more in potassium chloride, potash, potassium sulfate, potassium nitrate, sodium chloride, sodium carbonate, sodium sulphate, the sodium nitrate.
6. the preparation method of negative electrode active material according to claim 1, in the said step (3), the condition of calcining comprises that calcining heat is 500 ℃-700 ℃, calcination time is 3-16 hour.
7. the preparation method of negative pole according to claim 1, in the said step (1), solvent is an absolute ethyl alcohol.
8. the preparation method of nano barium titanate chromium lithium according to claim 1, the temperature of the drying in the wherein said step (2) is 100 ℃.
9. negative electrode active material; This negative electrode active material comprises nano barium titanate chromium lithium; The average grain diameter of said nano barium titanate chromium lithium is 200-250nm; The particle of nano barium titanate chromium lithium is octahedral structure, and this metatitanic acid chromium lithium prepares for the preparation method through the said any said negative electrode active material of claim 1-8.
10. lithium rechargeable battery; Comprise battery container in this battery and be contained in electric core and the nonaqueous electrolytic solution in the battery container; Fold or reel after said electric core is stacked by positive pole, barrier film, negative pole successively and form; It is characterized in that, contain the described negative electrode active material of claim 9 in the said negative pole.
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| CN103227320A (en) * | 2013-02-16 | 2013-07-31 | 东北大学 | Preparation method for iron lithium titanate positive electrode materials with titanium-containing nanotubes as raw material |
| CN103390746A (en) * | 2012-05-07 | 2013-11-13 | 电子科技大学 | Method for improving performance of lithium ion battery cathode material lithium titanate |
| CN104617285A (en) * | 2014-12-16 | 2015-05-13 | 天津大学 | Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method |
| CN105609321A (en) * | 2016-03-25 | 2016-05-25 | 陕西煤业化工技术研究院有限责任公司 | Lithium ion capacitor cathode composite material and preparation method thereof |
| CN105932272A (en) * | 2016-05-23 | 2016-09-07 | 渤海大学 | Preparation method of chromium lithium titanate nano-material |
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| CN106531991A (en) * | 2016-11-08 | 2017-03-22 | 华中科技大学 | Preparation method used for improving temperature tolerance of electrode materials |
| CN109616660A (en) * | 2018-12-23 | 2019-04-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Cobaltosic oxide is carried on preparation method of carbon nanosheet electrode material and products thereof and application |
| CN109904439A (en) * | 2017-12-11 | 2019-06-18 | 中信国安盟固利动力科技有限公司 | A kind of low temperature preparation method of novel titanium base material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919736A (en) * | 2006-08-17 | 2007-02-28 | 北京理工大学 | Preparation method of spinelle lithium titanate for lithium secondary battery negative electrode material |
| CN101000960A (en) * | 2006-12-29 | 2007-07-18 | 深圳市贝特瑞电子材料有限公司 | Composite lithium titanate electrode material and preparation method thereof |
| CN101567442A (en) * | 2008-07-28 | 2009-10-28 | 新乡市中科科技有限公司 | Method for preparing spinel lithium titanate |
| CN101624212A (en) * | 2008-07-10 | 2010-01-13 | 上海比亚迪有限公司 | Preparation method for lithium titanate composite material |
-
2010
- 2010-06-29 CN CN2010102188337A patent/CN102315427A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919736A (en) * | 2006-08-17 | 2007-02-28 | 北京理工大学 | Preparation method of spinelle lithium titanate for lithium secondary battery negative electrode material |
| CN101000960A (en) * | 2006-12-29 | 2007-07-18 | 深圳市贝特瑞电子材料有限公司 | Composite lithium titanate electrode material and preparation method thereof |
| CN101624212A (en) * | 2008-07-10 | 2010-01-13 | 上海比亚迪有限公司 | Preparation method for lithium titanate composite material |
| CN101567442A (en) * | 2008-07-28 | 2009-10-28 | 新乡市中科科技有限公司 | Method for preparing spinel lithium titanate |
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| CN103390746B (en) * | 2012-05-07 | 2016-08-03 | 电子科技大学 | A kind of method improving lithium ionic cell cathode material lithium titanate performance |
| CN103390746A (en) * | 2012-05-07 | 2013-11-13 | 电子科技大学 | Method for improving performance of lithium ion battery cathode material lithium titanate |
| CN103227320A (en) * | 2013-02-16 | 2013-07-31 | 东北大学 | Preparation method for iron lithium titanate positive electrode materials with titanium-containing nanotubes as raw material |
| CN104617285B (en) * | 2014-12-16 | 2017-02-22 | 天津大学 | Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method |
| CN104617285A (en) * | 2014-12-16 | 2015-05-13 | 天津大学 | Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method |
| CN105609321B (en) * | 2016-03-25 | 2018-07-31 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium-ion capacitor anode material and preparation method thereof |
| CN105609321A (en) * | 2016-03-25 | 2016-05-25 | 陕西煤业化工技术研究院有限责任公司 | Lithium ion capacitor cathode composite material and preparation method thereof |
| CN105932272A (en) * | 2016-05-23 | 2016-09-07 | 渤海大学 | Preparation method of chromium lithium titanate nano-material |
| CN105932272B (en) * | 2016-05-23 | 2018-11-13 | 渤海大学 | A kind of preparation method of metatitanic acid chromium lithium nano material |
| CN106374136A (en) * | 2016-08-26 | 2017-02-01 | 浙江长兴金太阳电源有限公司 | Overheat-proof diaphragm used for lithium ion batteries and preparation method thereof |
| CN106299203A (en) * | 2016-08-26 | 2017-01-04 | 浙江长兴金太阳电源有限公司 | A kind of lithium ion battery organo-mineral complexing barrier film and preparation method thereof |
| CN106531991A (en) * | 2016-11-08 | 2017-03-22 | 华中科技大学 | Preparation method used for improving temperature tolerance of electrode materials |
| CN106531991B (en) * | 2016-11-08 | 2019-05-21 | 华中科技大学 | A kind of durothermic preparation method of raising electrode material |
| CN109904439A (en) * | 2017-12-11 | 2019-06-18 | 中信国安盟固利动力科技有限公司 | A kind of low temperature preparation method of novel titanium base material |
| CN109616660A (en) * | 2018-12-23 | 2019-04-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Cobaltosic oxide is carried on preparation method of carbon nanosheet electrode material and products thereof and application |
| CN109616660B (en) * | 2018-12-23 | 2021-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cobaltosic oxide supported carbon nanosheet electrode material, product and application thereof |
| CN112408480A (en) * | 2020-11-30 | 2021-02-26 | 海南大学 | LiCrTiO with electrochemical oscillation effect4Preparation method of (1) |
| CN112408480B (en) * | 2020-11-30 | 2022-01-18 | 海南大学 | LiCrTiO with electrochemical oscillation effect4Preparation method of (1) |
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