CN1790799A - High power lithium ion battery and method for preparing amorphous carbon coated anode material - Google Patents
High power lithium ion battery and method for preparing amorphous carbon coated anode material Download PDFInfo
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- CN1790799A CN1790799A CNA2004100939618A CN200410093961A CN1790799A CN 1790799 A CN1790799 A CN 1790799A CN A2004100939618 A CNA2004100939618 A CN A2004100939618A CN 200410093961 A CN200410093961 A CN 200410093961A CN 1790799 A CN1790799 A CN 1790799A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for high-power lithium ion cell and amorphous-carbon to coat positive material. Wherein, the cell positive shell comprises a positive active material with shell-nucleus structure; the shell structure has amorphous material while the nucleus is spherical material with D50 size less than 10mum; the negative electrode comprises active material and carbon fiber, and the dual-surface coating weight for positive and negative active materials is 10-30mg/cm2 and 4.8-14.5mg/cm2 respectively. The method for amorphous-carbon comprises: 1) dipping the positive material into sweet water; 2) stirring, filtering; 3) drying; 4) carbonizing in inert gas atmosphere at 600-1000DEG C; 5) breaking and screening. This invention reduces internal resistance of electrode, increases discharge property of cell, and economical to process.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of high power lithium ion cell and prepare the method for amorphous carbon coated anode material.
Background technology
Advantages such as present known lithium ion battery is compared with secondary cells such as traditional plumbic acid, NI-G, ni-mhs, and lithium ion battery has high-energy-density, and self discharge is few have been widely used in electronic apparatuss such as mobile phone, notebook, video camera.Recently, along with hybrid vehicle, the high performance of various boost motors is needed a kind of high-power battery that can be used for said system badly.The representative battery that can satisfy above-mentioned requirements is a lithium ion battery.
Lithium ion battery is by negative plate, positive plate, electrolyte and prevent that between between positive/negative plate the barrier film of its short circuit from forming.For example, its negative plate is to be fixed on absorption on the collector/the emit carbonaceous material of lithium ion; Positive plate be fixed on absorption on the collector/emit lithium ion resemble composite oxides such as cobalt-lithium oxide; Electrolyte is to be dissolved with LiPF
6Deng the solution of aprotic organic solvent.
Aforementioned positive plate and negative plate be made into thin plate or paper tinsel shape, then battery lead plate and intervenient barrier film is stacked in order or helical form spooling and form electric core.Again this electric core pack in the iron or lighter aluminum metal case or lamination A1 flexible packaging film battery case of stainless steel, nickel plating, the electrolyte that reinjects, sealing and make battery.
Usually, corresponding with service condition, the various performance demands of battery are also changed, the high magnification of first battery is put, charging performance.Sometimes even require the battery can be at the above multiplying power discharging of 10C.But the commodity lithium ion battery of general conventional design can only be emitted about 80% of its nominal capacity when the 2C multiplying power discharging, and at all can not be at the 10C multiplying power discharging.Its main cause is that internal resistance is excessive.
Known at present, the multiplying power discharging or the specific power of raising lithium ion battery, the methods such as diffusion velocity that typically use electrolyte with high ionic conductivity or the electronic conductivity that improves pole plate and accelerate lithium ion.For reducing the resistance of pole plate, generally be to add a large amount of conductive agents, such as adding 10wt% even more acetylene black, but for guaranteeing that adhesion strength must add a large amount of binding agents simultaneously, this is little to reducing the internal resistance effect, just gets half the result with twice the effort.
Summary of the invention
The present invention provides a kind of high power lithium ion cell that satisfies low internal resistance, high-multiplying power discharge and the method for preparing amorphous carbon coated anode material for solving the problem that exists in the known technology.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is:
High power lithium ion cell comprises positive pole, and negative pole and electrolyte are characterized in: described positive pole comprises the positive electrode active materials of shell, nuclear structure, and described shell structure contains amorphous substance, and described nuclear is that a ball D50 particle diameter is not more than 10 microns sphere material; Described negative pole comprises negative active core-shell material and carbon fiber; The double spread weight of described positive electrode active materials and described negative active core-shell material is respectively 10-30mg/cm
2And 4.8-14.5mg/cm
2
Prepare the method for amorphous carbon coated anode material, be characterized in: may further comprise the steps 1. positive electrode is immersed in the sugar aqueous solution, filter out solution after 2. stirring, 3. dry, 4. carbonization under the inert gas atmosphere of 600-1000 ℃ of temperature, 5. grinding and sieving.
The present invention can also adopt following technical measures to realize:
High power lithium ion cell is characterized in: described positive electrode active materials is the cobalt-lithium oxide active material, and amorphous substance is an amorphous carbon in the described shell structure, and sphere material is a cobalt-lithium oxide in the described nuclear structure; A kind of active material of described negative active core-shell material for selecting from spherical graphite or flaky graphite, the content of described carbon fiber is greater than 1wt%, less than 5wt%.
High power lithium ion cell is characterized in: the composition formula of described positive electrode active materials is Li
xMO
2Or Li
yM
2O
4Composite oxides; M is one or more transition metal in the described formula, 0≤x in the described formula≤1,0≤y≤2.
High power lithium ion cell is characterized in: described positive electrode active materials is chalcogen compound or the oxide with tunnel or layer structure.
High power lithium ion cell is characterized in: compound also mixes Al or Mg element in the described positive electrode active materials.
High power lithium ion cell is characterized in: described positive electrode active materials is a conducting polymer composite in the organic compound.
High power lithium ion cell is characterized in: described all cpds can mix use.
High power lithium ion cell is characterized in: described positive pole contains the carbon nano-fiber that length is not more than 20 microns, and its addition is no more than 10wt% with respect to anodal coating gross weight.
Prepare the method for amorphous carbon coated anode material, be characterized in: described positive electrode is a cobalt-lithium oxide, and described syrup is the aqueous solution of 2: 3 pure white sugar of weight ratio or white granulated sugar and deionized water; Described stirring is that the mixer of 300rpm stirred 30 minutes; Described drying is 60 ℃ of air dryings 3 hours; Described inert gas atmosphere in continuous tunnel furnace, the displacement in 1 hour of logical Ar gas fall air in the thorax, then with mobile Ar protection divide three go on foot intensification from room temperature be raised to 100 ℃, again to 600 ℃, be warmed up to 700 ℃ of constant temperature 10 hours at last; Described pulverizing is ball mill grinding; Described sieving to crossing 300 mesh sieves.
Advantage and good effect that the present invention has are: owing to adopted the anodal positive electrode active materials that comprises shell, nuclear structure, described shell structure contains amorphous substance, described nuclear is that a ball D50 particle diameter is not more than 10 microns sphere material, described negative pole comprises negative active core-shell material and carbon fiber, make the electron conduction of electrode be improved, the ions diffusion distance is shortened simultaneously, thereby has reduced the internal resistance of cell, has realized the high-rate discharge capacity of lithium ion battery; Because the double spread weight of described positive electrode active materials and described negative active core-shell material is respectively 10-30mg/cm
2And 4.8-14.5mg/cm
2, on the surface of active material, form the good amorphous carbon shell of a kind of conductivity really, thereby improve anodal multiplying power discharging property.
Description of drawings
Fig. 1 is the SEM photo of embodiment of the invention high power lithium ion cell " core-shell structure " cobalt-lithium oxide;
Fig. 2 is the TG-DTA measurement result of embodiment of the invention high power lithium ion cell " core-shell structure " cobalt-lithium oxide;
Fig. 3 is the XRD spectra of embodiment of the invention high power lithium ion cell " core-shell structure " cobalt-lithium oxide.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, exemplify following examples now, and conjunction with figs. is described in detail as follows:
Embodiment 1, sees also Fig. 1-3: make A1, A2, A3, B1, B2 according to following concrete scheme, 5 kinds of batteries compare, and the preparation process of A1, A2, A3, B1 is:
The preparation of the cobalt-lithium oxide of core-shell structure: at first, prepared white sugar water solution.Promptly the edible pure white sugar of 200g is dissolved in the 300ml deionized water, makes transparent white sugar water solution.Next is to hang sugar, promptly the average D50 particle diameter of ball of 200g is respectively 2,5,10,15 microns LiCoO
2Powder joins in the above-mentioned white sugar water solution, with rotating speed be the homogenizer of 300rpm stir 30 minutes, suction filtration falls superfluous white sugar water solution, 60 ℃ of air dryings 3 hours then.Next be carbonization become shell, promptly dry extension sugar LiCoO
2Be put in the continuous tunnel furnace, air in the thorax is fallen in the displacement in 1 hour of logical Ar gas, then with the Ar protection of flowing divide three steps heat up from room temperature be raised to 100 ℃, again to 600 ℃, be warmed up to 700 ℃ of constant temperature at last and can obtain the LiCoO that carbon coats in 10 hours
2300 mesh sieves are crossed in ball mill grinding again, promptly become shown in Figure 1 having " core-shell structure " LiCoO
2The SEM photo.
For determining bag carbon amount, bag carbon front and back LiCoO
2Crystalline texture, the present invention adopted TG-DTA shown in Figure 2 figure and XRD analysis figure shown in Figure 3.TG-DTA figure shown in Figure 2 is that the covering amount of carbon as can be known is 1.1wt%; Wrap the carbon process as can be known to LiCoO by XRD result shown in Figure 3
2Crystalline texture do not have influence and because of the diffraction maximum that do not have 002 graphite face, can judge that carbon-coating is an impalpable structure.
The making of positive plate:
Take by weighing the LiCoO of the 93wt% of positive electrode active materials
2, the PVdF bonding agent nmp solution, and the content that makes PVdF is 4.5wt%, content as electric conducting material involucrum carbon+VGCF is 2.5wt%, the three is mixed the formation cathode mix, in mixture, add NMP and prepare pastel with mixer, then this pastel is coated onto equably the two sides that thickness is 20 μ m aluminium foils, again drying, roll-in and to make coating weight be 22mg/cm
2Positive plate.
The preparation of negative plate:
Carbonaceous mesophase spherules MCMB in weight 60%, 30% flaky graphite, the PVdF of the VGCF of weight 2% and weight 8%, wherein PVdF adds in the solution mode of NMP, make pastel, then this pastel is coated onto equably the two sides that thickness is 10 μ m Copper Foils, drying again, roll-in and make negative plate.Coating weight is 10mg/cm
2
The microporous polyethylene film that is about 25 microns with thickness is made diaphragm body.
The nonaqueous electrolyte that uses is for being dissolved with 1mol/l LiPF
6Volume ratio is the mixed solvent solution of 1: 1: 1 EC+DEC+DMC, adds relative electrolyte total amount on this basis, and vinylene carbonate content is 1.0wt%.
The assembling of battery (18650):
Stacked winding forms electric core, inserts cylinder, welds electrode in order, fluid injection is sealed again after 60 ℃ of vacuumize with above-mentioned positive pole, barrier film, negative pole.So be assembled into 18650 batteries as battery A1, A2, A3, B1, and carry out electro-chemical test as follows.
Charge-discharge test:
At first carried out volume test.Be charged as the CC-CV pattern; Discharge is the CC pattern.Promptly use 0.2C multiplying power constant current charge to 4.2V, the 4.2V constant voltage is 2 hours then; Discharge ends to 2.75V with 0.2C multiplying power constant current discharge equally.The discharge capacity that obtains in order to last method is as initial capacity, and discharge and likening to of charge capacity are efficiency for charge-discharge.Carry out the multiplying power discharging experiment then.Promptly same with volume test, all be charged to 4.2V with CC-CV, more respectively being equivalent to 0.5C, 1C, 2C, 5C, 10C, 15C constant current discharge are to 2.75V, with the capacity of this capacity that obtains as each multiplying power discharging.And, behind each multiplying power discharging, all treat again residual capacity to be carried out recharging after low range 0.2C discharges into 2.75V after voltage OCV recovers at every turn.The result who discharges and recharges by above method is organized in the table 1.
The preparation process of B2 is LiCoO
2Do not wrap carbon, that is:
The making of positive plate:
Take by weighing in the positive electrode active materials average D50 particle diameter of ball and be 2 microns LiCoO
2The LiCoO of the 93wt% of powder
2, the PVdF bonding agent nmp solution, and the content that makes PVdF is 4.5wt%, content as electric conducting material VGCF is 2.5wt%, the three is mixed the formation cathode mix, in mixture, add NMP and prepare pastel with mixer, then this pastel is coated onto equably the two sides that thickness is 20 μ m aluminium foils, again drying, roll-in and to make coating weight be 22mg/cm
2Positive plate.
The preparation of negative plate:
Carbonaceous mesophase spherules MCMB in weight 60%, 30% flaky graphite, the PVdF of the VGCF of weight 2% and weight 8%, wherein PVdF adds in the solution mode of NMP, make pastel, then this pastel is coated onto equably the two sides that thickness is 10 μ m Copper Foils, drying again, roll-in and make negative plate.Coating weight is 10mg/cm
2
The microporous polyethylene film that is about 25 microns with thickness is made diaphragm body.
The nonaqueous electrolyte that uses is for being dissolved with 1mol/l LiPF
6Volume ratio is the mixed solvent solution of 1: 1: 1 EC+DEC+DMC, adds relative electrolyte total amount on this basis, and vinylene carbonate content is 1.0wt%.The assembling of battery (18650):
Stacked winding forms electric core, inserts cylinder, welds electrode in order, fluid injection is sealed again after 60 ℃ of vacuumize with above-mentioned positive pole, barrier film, negative pole.So be assembled into 18650 batteries as battery B2, and carry out electro-chemical test as follows.
Charge-discharge test:
At first carried out volume test.Be charged as the CC-CV pattern; Discharge is the CC pattern.Promptly use 0.2C multiplying power constant current charge to 4.2V, the 4.2V constant voltage is 2 hours then; Discharge ends to 2.75V with 0.2C multiplying power constant current discharge equally.The discharge capacity that obtains in order to last method is as initial capacity, and discharge and likening to of charge capacity are efficiency for charge-discharge.Carry out the multiplying power discharging experiment then.Promptly same with volume test, all be charged to 4.2V with CC-CV, more respectively being equivalent to 0.5C, 1C, 2C, 5C, 10C, 15C constant current discharge are to 2.75V, with the capacity of this capacity that obtains as each multiplying power discharging.And, behind each multiplying power discharging, all treat again residual capacity to be carried out recharging after low range 0.2C discharges into 2.75V after voltage OCV recovers at every turn.The result who discharges and recharges by above method is organized in the table 1.
Table 1:
| Battery | LiCoO 2Particle diameter (um) | Bag carbon has or not | Initial capacity (mAh) | Efficiency for charge-discharge (%) | 0.5C | 1C | 2C | 5C | 10C | 15C |
| A1 | 2 | Have | 1408 | 90 | 100％ | 99％ | 98.2％ | 96％ | 91％ | 76％ |
| A2 | 5 | Have | 1422 | 91 | 100％ | 99％ | 98％ | 94％ | 87％ | 70％ |
| A3 | 10 | Have | 1415 | 92 | 100％ | 98％ | 94％ | 86％ | 75％ | 50％ |
| B1 | 15 | Have | 1422 | 92 | 100％ | 96％ | 91％ | 78％ | 60％ | 20％ |
| B2 | 2 | Do not have | 1406 | 91 | 100％ | 98％ | 90％ | 68％ | 30％ | - |
Can be clear that from the result of table 1: work as LiCoO
2Particle diameter when being no more than 10 microns, the 5C discharge is big difference very not; During the above multiplying power discharging of 10C, can find that then the capability retention of the more little big multiplying power discharging of particle diameter is high more, i.e. the LiCoO of small particle diameter
2Help big multiplying power current discharge.If but particle diameter is excessive, be that high-rate discharge ability more than 15 microns the 10C of B1 battery obviously reduces as using the D50 particle diameter.So LiCoO
2The D50 particle diameter to be not more than 10 microns for well.
In addition, relatively the big multiplying power discharging property of A1 and B2 battery as can be known, the high-rate discharge ability of A1 battery that wraps carbon is apparently higher than the comparison battery B2 that does not wrap carbon.So behind the bag carbon, to the big multiplying power current discharge properties that improves battery by significant effect.
Embodiment 2, make A1, A4, A5, B3, B4 according to following concrete scheme, and 5 kinds of batteries compare, and the preparation process of A1, A4, A5, B3 is:
The preparation of the cobalt-lithium oxide of core-shell structure: at first, prepared white sugar water solution.Promptly the edible pure white sugar of 200g is dissolved in the 300ml deionized water, makes transparent white sugar water solution.Next is to hang sugar, promptly the average D50 particle diameter of ball of 200g is respectively 2 microns LiCoO
2Powder joins in the above-mentioned white sugar water solution, with rotating speed be the homogenizer of 300rpm stir 30 minutes, suction filtration falls superfluous white sugar water solution, 60 ℃ of air dryings 3 hours then.Next be carbonization become shell, promptly dry extension sugar be put in the continuous tunnel furnace, air in the thorax is fallen in the displacement in 1 hour of logical Ar gas, then with the Ar protection of flowing divide three steps heat up from room temperature be raised to 100 ℃, again to 600 ℃, be warmed up to 700 ℃ of constant temperature at last and can obtain the LiCoO that carbon coats in 10 hours
2300 mesh sieves are crossed in ball mill grinding again, and are standby.
The making of positive plate:
Take by weighing the LiCoO of the 93wt% of positive electrode active materials
2, the PVdF bonding agent nmp solution, and the content that makes PVdF is 4.5wt%, content as electric conducting material involucrum carbon+VGCF is 2.5wt%, the three is mixed the formation cathode mix, in mixture, add NMP and prepare pastel with mixer, then this pastel is coated onto equably the two sides that thickness is 20 μ m aluminium foils, again drying, roll-in and to make coating weight be 22mg/cm
2, 10mg/cm
2, 30mg/cm
2, 45mg/cm
2Positive plate.
The preparation of negative plate:
Carbonaceous mesophase spherules MCMB in weight 60%, 30% flaky graphite, the PVdF of the VGCF of weight 2% and weight 8%, wherein PVdF adds in the solution mode of NMP, make pastel, then this pastel is coated onto equably the two sides that thickness is 10 μ m Copper Foils, drying again, roll-in and make negative plate.Coating weight is 10mg/cm
2, 4.8mg/cm
2, 14.5mg/cm
2, 22mg/cm
2
The microporous polyethylene film that is about 25 microns with thickness is made diaphragm body.
The nonaqueous electrolyte that uses is for being dissolved with 1mol/l LiPF
6Volume ratio is the mixed solvent solution of 1: 1: 1 EC+DEC+DMC, adds relative electrolyte total amount on this basis, and vinylene carbonate content is 1.0wt%.
The assembling of battery (18650):
Stacked winding forms electric core, inserts cylinder, welds electrode in order, fluid injection is sealed again after 60 ℃ of vacuumize with above-mentioned positive pole, barrier film, negative pole.So be assembled into 18650 batteries as battery A1, A4, A5, B3, and carry out electro-chemical test as follows.
Charge-discharge test:
At first carried out volume test.Be charged as the CC-CV pattern; Discharge is the CC pattern.Promptly use 0.2C multiplying power constant current charge to 4.2V, the 4.2V constant voltage is 2 hours then; Discharge ends to 2.75V with 0.2C multiplying power constant current discharge equally.The discharge capacity that obtains in order to last method is as initial capacity, and discharge and likening to of charge capacity are efficiency for charge-discharge.Carry out the multiplying power discharging experiment then.Promptly same with volume test, all be charged to 4.2V with CC-CV, more respectively being equivalent to 0.5C, 1C, 2C, 5C, 10C, 15C constant current discharge are to 2.75V, with the capacity of this capacity that obtains as each multiplying power discharging.And, behind each multiplying power discharging, all treat again residual capacity to be carried out recharging after low range 0.2C discharges into 2.75V after voltage OCV recovers at every turn.The result who discharges and recharges by above method is organized in the table 2.
The preparation process of B4 is LiCoO
2Do not wrap carbon, that is:
The making of positive plate:
Take by weighing in the positive electrode active materials average D50 particle diameter of ball and be 2 microns LiCoO
2The LiCoO of the 93wt% of powder
2, the PVdF bonding agent nmp solution, and the content that makes PVdF is 4.5wt%, content as electric conducting material VGCF is 2.5wt%, the three is mixed the formation cathode mix, in mixture, add NMP and prepare pastel with mixer, then this pastel is coated onto equably the two sides that thickness is 20 μ m aluminium foils, again drying, roll-in and to make coating weight be 45mg/cm
2Positive plate.
The preparation of negative plate:
Carbonaceous mesophase spherules MCMB in weight 60%, 30% flaky graphite, the PVdF of the VGCF of weight 2% and weight 8%, wherein PVdF adds in the solution mode of NMP, make pastel, then this pastel is coated onto equably the two sides that thickness is 10 μ m Copper Foils, drying again, roll-in and make negative plate.Coating weight is 22mg/cm
2
The microporous polyethylene film that is about 25 microns with thickness is made diaphragm body.
The nonaqueous electrolyte that uses is for being dissolved with 1mol/l LiPF
6Volume ratio is the mixed solvent solution of 1: 1: 1 EC+DEC+DMC, adds relative electrolyte total amount on this basis, and vinylene carbonate content is 1.0wt%.
The assembling of battery (18650):
Stacked winding forms electric core, inserts cylinder, welds electrode in order, fluid injection is sealed again after 60 ℃ of vacuumize with above-mentioned positive pole, barrier film, negative pole.So be assembled into 18650 batteries as battery B4, and carry out electro-chemical test as follows.
Charge-discharge test:
At first carried out volume test.Be charged as the CC-CV pattern; Discharge is the CC pattern.Promptly use 0.2C multiplying power constant current charge to 4.2V, the 4.2V constant voltage is 2 hours then; Discharge ends to 2.75V with 0.2C multiplying power constant current discharge equally.The discharge capacity that obtains in order to last method is as initial capacity, and discharge and likening to of charge capacity are efficiency for charge-discharge.Carry out the multiplying power discharging experiment then.Promptly same with volume test, all be charged to 4.2V with CC-CV, more respectively being equivalent to 0.5C, 1C, 2C, 5C, 10C, 15C constant current discharge are to 2.75V, with the capacity of this capacity that obtains as each multiplying power discharging.And, behind each multiplying power discharging, all treat again residual capacity to be carried out recharging after low range 0.2C discharges into 2.75V after voltage OCV recovers at every turn.The result who discharges and recharges by above method is organized in the table 2.
Table 2:
| Battery | Coating weight (mg/cm 2) | Initial capacity (mAh) | Efficiency for charge-discharge (%) | 0.5C | 1C | 2C | 5C | 10C | 15C | |
| Anodal | Negative pole | |||||||||
| A1 | 22 | 10 | 1408 | 90 | 100％ | 99％ | 98.2％ | 96％ | 91％ | 76％ |
| A4 | 10 | 4.8 | 1103 | 89.6 | 100％ | 100％ | 99.6％ | 98％ | 96％ | 90％ |
| A5 | 30 | 14.5 | 1635 | 91 | 100％ | 98.2％ | 94.2％ | 90％ | 83％ | 61％ |
| B3 | 45 | 22 | 2217 | 91 | 100％ | 97％ | 90％ | 70％ | 32％ | - |
| B4 | 45 | 22 | 2238 | 91 | 99％ | 96％ | 87％ | 54％ | 11％ | - |
Can know clearly from the result of table 2: coating weight is very big to the influence of multiplying power.The few more multiplying power discharging property of coating weight good more but when the coating weight comparative example B3 close with the coating weight of the present lithium ion battery of circulation as can be known during the 2C discharge and battery of the present invention do not have tangible difference but can find that its capability retention can not discharge far below battery of the present invention and its during when the above multiplying power discharging of 5C at all under 15C multiplying power electric current.It is poorer to see that simultaneously its discharge performance of conventional batteries B4 of carbon is not wrapped in use again.So behind the bag carbon, to the big multiplying power current discharge properties that improves battery by significant effect.Simultaneously, coating weight also very necessary, be that the few more multiplying power discharging property of coating weight is good more; But the coating weight of influence, both positive and negative polarity of considering the energy density of battery and coating process precision is to be controlled at 10mg-30mg/cm respectively
2, 4.8mg-14.5mg/cm
2For good.
Embodiment 3, make A1, A6, A7, A8, B5, B6 according to following concrete scheme, and 5 kinds of batteries compare, and the preparation process of A1, A6, A7, B8 is:
The preparation of the cobalt-lithium oxide of core-shell structure: at first, prepared white sugar water solution.Promptly the edible pure white sugar of 200g is dissolved in the 300ml deionized water, makes transparent white sugar water solution.Next is to hang sugar, promptly the average D50 particle diameter of ball of 200g is respectively 2 microns LiCoO
2Powder joins in the above-mentioned white sugar water solution, with rotating speed be the homogenizer of 300rpm stir 30 minutes, suction filtration falls superfluous white sugar water solution, 60 ℃ of air dryings 3 hours then.Next be carbonization become shell, promptly dry extension sugar be put in the continuous tunnel furnace, air in the thorax is fallen in the displacement in 1 hour of logical Ar gas, then with the Ar protection of flowing divide three steps heat up from room temperature be raised to 100 ℃, again to 600 ℃, be warmed up to 700 ℃ of constant temperature at last and can obtain the LiCoO that carbon coats in 10 hours
2300 mesh sieves are crossed in ball mill grinding again, promptly become shown in Figure 1 having " core-shell structure " LiCoO
2The SEM photo.
For determining bag carbon amount, bag carbon front and back LiCoO
2Crystalline texture, the present invention adopted TG-DTA shown in Figure 2 figure and XRD analysis figure shown in Figure 3.TG-DTA figure shown in Figure 2 is that the covering amount of carbon as can be known is 1.1wt%; Wrap the carbon process as can be known to LiCoO by XRD result shown in Figure 3
2Crystalline texture do not have influence and because of the diffraction maximum that do not have 002 graphite face, can judge that carbon-coating is an impalpable structure.
The making of positive plate:
The proportioning of battery A1, A7, the anodal coating of B5 is LiCoO
2: PVdF: shell carbon+VGCF=93: 4.5: 2.5; The proportioning of the anodal coating of battery A6, A8 is LiCoO
2: PVdF: shell carbon+VGCF=87: 7: 6; Do not add VGCF in the battery B6 positive pole, the component suitable with VGCF made into active material; Prepare pastel with mixer, then this pastel is coated onto equably the two sides that thickness is 20 μ m aluminium foils, again drying, roll-in and to make coating weight be 22mg/cm
2Positive plate.
The preparation of negative plate:
The addition of battery A1, A6 negative pole VGCF is 2Wt%; The addition of A7, A8 negative pole VGCF is 5Wt%; Do not add VGCF in B5, the B6 negative pole, and the B6 handle component suitable with VGCF made active material into; Carbonaceous mesophase spherules MCMB in weight 60%, 30% flaky graphite, the PVdF of the VGCF of weight 2Wt% and weight 8%, wherein PVdF adds in the solution mode of NMP, make pastel, then this pastel is coated onto equably the two sides that thickness is 10 μ m Copper Foils, drying again, roll-in and make negative plate.Coating weight is 10mg/cm
2
The microporous polyethylene film that is about 25 microns with thickness is made diaphragm body.
The nonaqueous electrolyte that uses is for being dissolved with 1mol/l LiPF
6Volume ratio is the mixed solvent solution of 1: 1: 1 EC+DEC+DMC, adds relative electrolyte total amount on this basis, and vinylene carbonate content is 1.0wt%.The assembling of battery (18650):
Stacked winding forms electric core, inserts cylinder, welds electrode in order, fluid injection is sealed again after 60 ℃ of vacuumize with above-mentioned positive pole, barrier film, negative pole.So be assembled into 18650 batteries as battery A1, A6, A7, A8, B5, B6, and carry out electro-chemical test as follows.
Charge-discharge test:
At first carried out volume test.Be charged as the CC-CV pattern; Discharge is the CC pattern.Promptly use 0.2C multiplying power constant current charge to 4.2V, the 4.2V constant voltage is 2 hours then; Discharge ends to 2.75V with 0.2C multiplying power constant current discharge equally.The discharge capacity that obtains in order to last method is as initial capacity, and discharge and likening to of charge capacity are efficiency for charge-discharge.Carry out the multiplying power discharging experiment then.Promptly same with volume test, all be charged to 4.2V with CC-CV, more respectively being equivalent to 0.5C, 1C, 2C, 5C, 10C, 15C constant current discharge are to 2.75V, with the capacity of this capacity that obtains as each multiplying power discharging.And, behind each multiplying power discharging, all treat again residual capacity to be carried out recharging after low range 0.2C discharges into 2.75V after voltage OCV recovers at every turn.The result who discharges and recharges by above method is organized in the table 3.
Table 3:
| Battery | VGCF | Initial capacity (mAh) | Efficiency for charge-discharge (%) | 0.5C | 1C | 2C | 5C | 10C | 15C |
| A1 | Just: 1.4% is negative: 2% | 1408 | 90 | 100％ | 99％ | 98.2％ | 96％ | 91％ | 76％ |
| A6 | Just: 4.9% is negative: 2% | 1322 | 89 | 100％ | 100％ | 99％ | 97％ | 93％ | 85％ |
| A7 | Just: 1.4% is negative: 5% | 1307 | 87 | 100％ | 99％ | 98.5％ | 96％ | 92％ | 81％ |
| A8 | Just: 4.9% is negative: 5% | 1200 | 86 | 100％ | 100％ | 100％ | 98％ | 94％ | 87％ |
| B5 | Just: 1.4% is negative: 0% | 1412 | 91 | 100％ | 98％ | 97％ | 91％ | 82％ | 65％ |
| B6 | Just: 0% is negative: 0% | 1509 | 92 | 100％ | 98％ | 96％ | 88％ | 79％ | 38％ |
Can be clear that from the result of table 3: no matter be the interpolation of positive pole or negative pole, VGCF when improving the above high-multiplying power discharge of 10C of battery capability retention and also to add VGCF in right amount especially effective more.So the interpolation of VGCF has significant effect to the big multiplying power current discharge properties that improves battery.
By adopting both positive and negative polarity of the present invention, the electron conduction of electrode is improved, and the ions diffusion distance is shortened simultaneously, thereby has reduced the internal resistance of cell, has realized the high-rate discharge capacity of lithium ion battery.
Though the above-mentioned cobalt-lithium oxide that adopted is as positive electrode active materials, the present invention is not limited in cobalt-lithium oxide, and the composition formula that can be used for positive electrode active materials of the present invention is Li
xMO
2, Li
yM
2O
4, M is more than one transition metal in the formula, the chalcogen compound or the oxide of the composite oxides of 0≤x≤1,0≤y≤2, tunnel or layer structure.Its instantiation can be enumerated as LiNiO
2, LiCo
xNi
1-xO
2, LiNi
xCo
yMn
1-x-yO
2, LiMn
2O
4, Li
2Mn
2O
4, LiNi
0.5Mn
1.5O
4,, LiFePO
4, MnO
2, FeO
2, V
2O
5, V
6O
13, TiO
2, TiS
2Deng.Certainly the derivative that also comprises the above-claimed cpd that elements such as Al, Mg mix.In addition, organic compound also can be used as positive electrode active materials of the present invention such as conducting polymers such as polypyrrole, polyanilines.And no matter be inorganic compound or organic compound, above-mentioned all cpds also can mix use.
As lithium ion battery of the present invention, it is characterized in that positive pole comprises the carbon nano-fiber of failing to grow up in 20 microns, and its addition is no more than 10wt% with respect to anodal coating gross weight.
This is because a certain amount of by adding, the carbon nano-fiber of certain-length, can fully guarantee in the electrode between active material and and collector between conductivity.Simultaneously, can make that again the combination property of electrode is guaranteed.The length of fiber surpasses 20 microns, then might make the part fiber pass barrier film and arrive electrode, causes the micro-short circuit between positive/negative plate.In addition, if addition surpasses 10wt%, then must add the adhesive force that a large amount of binding agents could keep electrode material layer simultaneously.Excessive binding agent then is the reason that causes the electrode internal resistance to raise.Therefore, the addition of carbon nano-fiber is to be no more than 10wt% for well.
The present invention exemplifies is gas-phase grown nanometer carbon fibre VGCF, also carbon black, acetylene black AB and stable metal nano fiber such as Ni etc. in addition.Optimum fiber shape electric conducting material.Because fibrous electric conducting material is suitable for the conduction approach of keeping.
The present invention has the amorphous carbon shell of the cobalt-lithium oxide active material of core-shell structure, is by hanging sugar, 600-1000 ℃ temperature, and Ar or N
2Make Deng carbonization under the reactive atmosphere not.This manufacture method economy, easy.And can on the surface of active material, form the good amorphous carbon shell of a kind of conductivity really, thereby improve anodal multiplying power discharging property.If heating-up temperature is lower than 600 ℃, then can not guarantee the carbonization of sugar; If be higher than 1000 ℃, then can cause carbon-coating to LiCoO
2Reduction, or the escape of part lithium.So preferred heating-up temperature is 600-1000 ℃, and serve as better with 650-800 ℃.In addition, to select Ar or N2 for use be for fear of oxidation of coal and with CO or CO to the protection gas of carbonization
2Form loss.Certainly the method for bag carbon also can methane, tar etc. prepares for carbon source, method by chemical vapor deposition (CVD).
Though lifted spherical graphite and scale shape graphite, can be used for that negative active core-shell material of the present invention is not limited only to this, other can be listed below as can be used for negative material class of the present invention, can form the metallic element such as the Al of alloy with Li, Si, Pb, Sn, Zn etc., transition metal oxide such as NiO, CoO, Co
2O
3, CuO etc., also have LiFe
2O
3, Nb
2O
3, WO
2, MoO
2,, the metal oxide of SiO etc., the easily carbonaceous material of graphitized carbon material and hard carbon etc. and the mixture of above-mentioned material.That considers battery discharges and recharges life-span and fail safe, preferred carbonaceous material.
As electrolyte of the present invention, can comprise one or more mixture of following organic solvent.Ethyl carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC), diethyl carbonate (DEC), gamma-butyrolacton (GBL), sulfolane, methyl-sulfoxide, second moon green grass or young crops (AN), dimethyl formamide, diethylformamide, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, oxolane (THF), 2-methyltetrahydrofuran, dioxolanes, methyl acetic acid ester isopolarity solvent.For obtaining good cell discharge performance and life-span, preferably make and in above-mentioned solvent, contain ethylene carbonate (EC).
The electrolytic salt that is dissolved in the electrolyte solvent can comprise following single electrolytic salt and composition thereof.LiPF for example
6, LiClO
4, LiBF
4, LiAsF
6, LiCF
3CO
2, LiCF
3(CF)
3, LiCF
3(C
2F
5)
3, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiN (SO
2CF
2CF
3)
2, LiN (COCF
3)
2, LiN (COCF
2CF
3)
2And LiPF
3(CF
2CF
3)
3Be preferably in and partly contain LiPF in the electrolytic salt
6Or LiBF
4, and can on negative pole, form good epithelium and obtain good flash-over characteristic and life-span.
Simultaneously for the transition that suppresses irreversible capacity and negative material surface SEI epithelium grow up, preferably add additive such as vinylene carbonate (VC) and derivative thereof, as 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, 4,5-dipropyl vinylene carbonate, 4-ethyl-5-methyl carbonic acid vinylene, 4-ethyl-5-propyl group vinylene carbonate.Annular in addition sulfuric ester also helps forming good SEI, as glycol sulfate, 1,2-propylene glycol sulfuric ester, 1,2-butanediol sulfuric ester, 1,3-butanediol sulfuric ester, 2,3-butanediol, benzoglycols sulfuric ester etc.
Slider of the present invention can adopt braid, non-woven fabric, micropore synthetic resin film etc.In the above-mentioned diaphragm material, the polyolefin micro-porous film of special preferred microporous synthetic resin film, especially preferably polyethylene and microporous polypropylene membrane or their composite micro porous film etc.The adopted reason of these TPO micro-porous films is that it is better than thickness preferably, film-strength, film resistance characteristic.
If the employing colloidal electrolyte, then it can doublely do separator again.In this case, can use porose copolymer solid electrolyte, make it contain electrolyte again.
Battery of the present invention can be made into column type, oval, square, button shaped and the folded film flexible package of A1 etc.Capacity can be tens of mAh to tens of Ah even more than the 100Ah.But when making high capacity lithium ion battery, with column type, oval, square for well.
Claims (10)
1. high power lithium ion cell, comprise positive pole, negative pole and electrolyte is characterized in that: described positive pole comprises the positive electrode active materials of shell, nuclear structure, described shell structure contains amorphous substance, and described nuclear is that a ball D50 particle diameter is not more than 10 microns sphere material; Described negative pole comprises negative active core-shell material and carbon fiber; The double spread weight of described positive electrode active materials and described negative active core-shell material is respectively 10-30mg/cm
2And 4.8-14.5mg/cm
2
2. high power lithium ion cell according to claim 1 is characterized in that: described positive electrode active materials is the cobalt-lithium oxide active material, and amorphous substance is an amorphous carbon in the described shell structure, and sphere material is a cobalt-lithium oxide in the described nuclear structure; A kind of active material of described negative active core-shell material for selecting from spherical graphite or flaky graphite, the content of described carbon fiber is greater than 1wt%, less than 5wt%.
3. high power lithium ion cell according to claim 1 is characterized in that: the composition formula of described positive electrode active materials is Li
xMO
2Or Li
yM
2O
4Composite oxides; M is one or more transition metal in the described formula, 0≤x in the described formula≤1,0≤y≤2.
4. high power lithium ion cell according to claim 1 is characterized in that: described positive electrode active materials is chalcogen compound or the oxide with tunnel or layer structure.
5. high power lithium ion cell according to claim 3 is characterized in that: compound also mixes Al or Mg element in the described positive electrode active materials.
6. high power lithium ion cell according to claim 1 is characterized in that: described positive electrode active materials is a conducting polymer composite in the organic compound.
7. according to each described high power lithium ion cell in the claim 1 to 6, it is characterized in that: described all cpds can mix use.
8. high power lithium ion cell according to claim 1 is characterized in that: described positive pole contains the carbon nano-fiber that length is not more than 20 microns, and its addition is no more than 10wt% with respect to anodal coating gross weight.
9. one kind prepares claim 1 or the 2 described methods that prepare amorphous carbon coated anode material, it is characterized in that: may further comprise the steps 1. positive electrode is immersed in the sugar aqueous solution, 2. filter out solution after stirring, 3. dry, 4. carbonization under the inert gas atmosphere of 600-1000 ℃ of temperature, 5. grinding and sieving.
10. the method for preparing amorphous carbon coated anode material according to claim 9 is characterized in that: described positive electrode is a cobalt-lithium oxide, and described syrup is the aqueous solution of 2: 3 pure white sugar of weight ratio or white granulated sugar and deionized water; Described stirring is that the mixer of 300rpm stirred 30 minutes; Described drying is 60 ℃ of air dryings 3 hours; Described inert gas atmosphere in continuous tunnel furnace, the displacement in 1 hour of logical Ar gas fall air in the thorax, then with mobile Ar protection divide three go on foot intensification from room temperature be raised to 100 ℃, again to 600 ℃, be warmed up to 700 ℃ of constant temperature 10 hours at last; Described pulverizing is ball mill grinding; Described sieving to crossing 300 mesh sieves.
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|---|---|---|---|
| CNA2004100939618A CN1790799A (en) | 2004-12-14 | 2004-12-14 | High power lithium ion battery and method for preparing amorphous carbon coated anode material |
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| CN100452491C (en) * | 2006-08-10 | 2009-01-14 | 武汉大学 | Granular electrode composite material with positive temp coefficient and preparing process thereof |
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| CN102332569A (en) * | 2011-03-22 | 2012-01-25 | 东莞新能源科技有限公司 | Lithium ion battery and negative electrode active material thereof |
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| CN106290989A (en) * | 2016-07-25 | 2017-01-04 | 四川理工学院 | A kind of atomic force microscope probe tip modification method |
| CN106848189A (en) * | 2017-01-23 | 2017-06-13 | 北京鼎能开源电池科技股份有限公司 | A kind of preparation method of high-density lithium ion battery pole piece |
| CN110190247A (en) * | 2018-02-23 | 2019-08-30 | 丰田自动车株式会社 | The manufacturing method of solid secondary battery system |
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