CN1225196A - Cathode material for lithium ion secondary battery, method for manufacturing the same, and lithium ion secondary battery using the same - Google Patents
Cathode material for lithium ion secondary battery, method for manufacturing the same, and lithium ion secondary battery using the same Download PDFInfo
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- CN1225196A CN1225196A CN97196220A CN97196220A CN1225196A CN 1225196 A CN1225196 A CN 1225196A CN 97196220 A CN97196220 A CN 97196220A CN 97196220 A CN97196220 A CN 97196220A CN 1225196 A CN1225196 A CN 1225196A
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Abstract
A cathode material for lithium secondary batteries which eliminates the disadvantageous of the conventional graphite materials and amorphous materials maintains the advantages of the materials, withstands overdischarge, has a small size and a light weight, and is high in energy density. The cathode material is a graphitized carbon material prepared by heat-treating a carbon material block containing boron or a boron compound (containing 3-20 wt.% of boron, preferably, a boron oxide) and crushing the block into particles, and adjusting the particle size of the particles. The size Lc of crystallites in the c-axis direction is more than 100 nm and in the a-axis direction less than 100 nm. In a method for manufacturing the cathode material, a mixture prepared by adding the power of the boron compound to a carbon material at a ratio of 3-20 wt.% in terms of boron is blocked and the blocks are heat-treated at a temperature above 2,400 DEG C in a reducing or inert gas atmosphere, and then, the obtained graphitized carbon material blocks are crushed into particles with a crushing means with which the blocks crushed in the a-axis direction rather than in the c-axis direction, and the particle size of the particles is adjusted.
Description
Invention field
The lithium ion secondary battery negative pole that the invention relates to doping, dedoping lithium ion is with material and manufacture method thereof and the lithium rechargeable battery that uses this negative material.
Background of invention
In recent years, along with miniaturization, the lightweight of electrical equipment and electronic instrument, development and exploitation have been accelerated to the secondary cell of small-sized, light weight, high-energy-density.As the part of this achievement in research, with LiCoO
2Be subjected to people's special concern Deng lithium rechargeable battery (hereinafter to be referred as " lithium secondary battery ") as positive active material, negative pole use carbon materials.
That lithium secondary battery is realized is small-sized, one of the key of high capacity is the carbon materials as negative material, at present, for new, effectively negative pole constantly deeply carries out with the research of carbon materials.This negative pole has a variety of with the existence form of carbon materials, for example graphite and coke, carbon black, active carbon, carbon fibre etc.Only just have native graphite, Delanium and kish etc. multiple with regard to a kind of material of graphite, and native graphite is also different along with its place of production different performance, Delanium depends on initiation material and heat treatment temperature etc., and performance has very big-difference.In brief, carbon materials has varied, and its property difference is very big.Therefore this means that the characteristic of the negative material of lithium secondary battery also is extremely diversified, be difficult to prediction, bring very big difficulty to negative pole with the research and development of carbon materials.
The negative pole of existing lithium secondary battery considers roughly can be divided into graphite based material and noncrystalline based material with carbon materials (hereinafter to be referred as " negative material ") from the angle of crystal structure.The graphite based material, Delanium that obtains 3000 ℃ of following heat treatments as native graphite with coke etc. has the structure of highly crystallineization.Use graphite based material is little as the irreversible capacity that negative material has the initial stage circulation, discharge potential is smooth, density is big thereby the capacity advantages of higher.On the other hand, it also has cycle characteristics simultaneously and quick charge is poor, and discharge potential is smooth, thereby is difficult to show shortcomings such as residual capacity.
In addition, the material of noncrystalline system is handled the coke of resulting carbide, pitch system or oil system etc. under 1000 ℃ as synthetic resin such as furfuryl alcohol, phenolic resins, have the inadequate structure of crystallization.When using the noncrystalline based material as lithium secondary battery cathode material, have cycle characteristics good, can show the battery residual capacity, can make advantages such as battery above theoretical capacity.Otherwise the irreversible capacity that this material also has initial stage circulation is big, discharge potential changes, owing to be that noncrystalline material thereby the minor variations when making all can produce a very large impact, cause shortcomings such as performance generation deviation to performance.
As mentioned above, the existing lithium secondary battery cathode material negative electrode for lithium secondary battery material that is used as small-sized, light weight, high-energy-density promptly has advantage that shortcoming is also arranged.Can to replace existing lithium secondary battery cathode material in order developing, do not have above-mentioned shortcoming, to be particularly suitable for the lithium secondary battery cathode material of desired secondary battery cathode material, the inventor has carried out experimental study repeatedly, and the result has finished the present invention.
Promptly, the objective of the invention is, the advantage of the graphite system that can give full play to simultaneously in the past and noncrystalline based material is provided and eliminates their shortcoming and strong lithium secondary battery cathode material and the manufacture method thereof of anti-overdischarge and lithium secondary batteries that uses this negative material separately.
Summary of the invention
In order to achieve the above object, the inventor is research experiment repeatedly, found that, as long as in carbon materials, add an amount of boron or boride, heat-treat behind the briquet, then the bulk material after the heat treatment is carried out suitable pulverizing, just can obtain to give full play to simultaneously the graphite system and the advantage of noncrystalline based material in the past and eliminate their shortcoming and strong lithium secondary battery cathode materials of anti-overdischarge separately.
Particularly, by pulverizing control, crystal structure through heat treated bulk material is applied specific influence, can obtain effective lithium secondary battery cathode material, by the addition and the kind thereof of further qualification boron or boron compound, can obtain the lithium secondary battery cathode material of better effects if.
The present invention finishes on the basis of above-mentioned opinion after further research.Wherein, the lithium secondary battery cathode material of the 1st invention is that the carbon materials piece that contains boron or boron compound is heat-treated, adjusted granularity then and the graphitized carbon cellulosic material that obtains, it is characterized in that, the axial big or small Lc of the c of crystallite is more than 100nm, and the axial big or small La of a is below 100nm.Adopt such negative material as lithium secondary battery cathode material, can give full play to the graphite based material and the advantage of noncrystalline based material in the past simultaneously and eliminate their shortcomings separately.
The 2nd invention is characterised in that in above-mentioned the 1st invention, the ratio that exists of the boron compound in the graphitized carbon cellulosic material is in 3-20% (weight) scope with boron calculating.Adopt this lithium secondary battery cathode material, except the effect described in above-mentioned the 1st invention, can guarantee the stability of current potential, realize the more lithium secondary battery of high capacity simultaneously.
The feature of the 3rd invention is that in above-mentioned the 1st invention, described boron compound uses the oxide of boron.Adopt such negative material, except the effect of the above-mentioned the 1st and the 2nd invention, can obtain the more lithium secondary battery of high power capacity.
The 4th invention is characterised in that as the lithium secondary battery cathode material in the 3rd invention of 1-, its flash-over characteristic is, at 1.3V[VvsLi/Li
+] above discharge capacity [mAh/g] is equivalent to 0-0.25V[VvsLi/Li
+] more than 1% of discharge capacity [mAh/g].That is to say to have the advantage of graphite based material in the past, promptly at 0.25V[VvsLi/Li
+] following current potential flatness and at 1.3V[VvsLi/Li
+] more than have the discharge capacity more than 1% that is equivalent to the following discharge capacity of 0.25V, thereby can form the strong lithium secondary battery cathode material of anti-overdischarge.
The 5th invention is the manufacture method of lithium secondary battery cathode material, it is characterized in that, in carbon materials, add the boron compound powder that calculates 3-20% (weight) with boron, after the gained mixture made piece, heat-treat under the temperature in reducing atmosphere or inert gas atmosphere and more than 2400 ℃, adopt the axial fracture of a kind of a of making to peel off more incidental breaking method graphited carbon materials piece is carried out the granularity adjustment than c is axial.Adopt this manufacture method, can obtain to give full play to simultaneously the graphite system and the advantage of noncrystalline based material in the past effectively and eliminate the lithium secondary battery cathode material of their shortcomings separately.
The feature of the manufacture method of the 6th invention is, in above-mentioned the 5th invention, described " making the fracture of graphited carbon materials piece on a direction of principal axis than the more incidental breaking method of peeling off on the c direction of principal axis " is, with graphited carbon materials block cooling, pulverizes then in advance.Adopt such cooling, breaking method, except the effect of above-mentioned the 5th invention, can obtain lithium secondary battery cathode material more economically.
The feature of the 7th invention is that in above-mentioned the 6th invention, described " pre-cooled " is to cool off with liquid nitrogen in advance.The method that employing is cooled off, pulverized by liquid nitrogen can obtain reliablely and stablely realizing the lithium secondary battery cathode material of the effect of the 6th invention.
In addition, the feature of the lithium secondary battery of the 8th invention is to use the negative pole of the 4th invention of above-mentioned 1-to use material as negative electrode active material.Adopt such lithium secondary battery cathode material, can be given full play to the graphite system and the advantage of noncrystalline based material in the past simultaneously and eliminate their shortcoming and good especially lithium secondary batteries of anti-overdischarge separately.
Explain the present invention below.
At first, as carbon materials, as aggregate, in this aggregate, add binding agent and boron (3-20 weight %) or boron compounds (being converted into boron is 3-20 weight %) such as pitch with the coke adjusted through granularity as required, green coke, graphite etc., carry out mixing then.Utilize mould that resulting mixing thing is shaped and be suitable block, under the temperature in reducing atmosphere or inert gas atmosphere, more than 2400 ℃ this block is heat-treated.The heat treated graphitized carbon cellulosic material of resulting process block is carried out the described specific pulverizing in back, become needed granularity by adjustment such as classifications then, obtain desirable lithium secondary battery cathode material.
The interpolation of boron or boron compound not necessarily must be carried out simultaneously with the interpolation of binding agent such as pitch, also can add in the operation that the mixing thing of graphite and pitch etc. is pulverized, mixed.In addition, described boron compound can be enumerated B
4C, BN and B
2O
3Deng B
XO
Y(x=1-8, y=1-8) compound or this compound are with the product of 1-8 valency positive and negative ionization (H for example
3BO
3) wait the oxide of boron.Wherein,,, can form small pore, obtain having the graphitized carbon cellulosic material block of the higher crystal structure of the doping effect of lithium by in heat treatment process, carrying out the oxidation of appropriateness if use the oxide of boron.
As the addition of boron compound, the boron compound in the graphitized carbon cellulosic material after the heat treatment to have ratio (calculating with boron) be in 3-20% (weight) scope.Be lower than at 3% o'clock, the graphited effect of the promotion that can not obtain expecting, otherwise, surpass at 20% o'clock, have a large amount of boron carbides in the graphitized carbon cellulosic material after the heat treatment, discharge capacity significantly reduces, the beneficial effect that promptly adds boron and produced exhausts, and the performance of battery descends significantly.Preferred range is 3-10% (weight), promptly, addition was less than 10% o'clock, can give full play to and add the effect of improving crystal structure that boron produced, make the ratio of the boron carbide that exists in the graphitized carbon cellulosic material after the heat treatment reduce to minimum simultaneously, thereby its adverse effect for battery performance is reduced to minimum level.
In addition, when atmosphere reducing atmosphere when forming heat treatment or inert gas atmosphere, as long as the carbon materials of secondary battery cathode material is not had negative influence, the mode of its formation without limits.For example, can use the gas that produces by binding agents such as pitches or argon gas etc. to form above-mentioned atmosphere.In addition, described in hereinafter, with heat treatment temperature be decided to be more than 2400 ℃ be because, the carbon materials that obtains in heat treatment more than 2400 ℃, the basal spacing d that records through X-ray diffraction
002Be 0.335nm, the P of magnificent Lun Shi (Warren)
1Value (the most contiguous hexagonal lattice plane is the probability that graphite is piled up) is 1, demonstrates desirable hexagonal crystal system graphite-structure.
The following describes the breaking method of the graphitized carbon cellulosic material block after the heat treatment.The inventor thinks, in order to obtain the graphitized carbon cellulosic material of lithium doping, crystal structure that the dedoping effect is higher, in general, the c direction of principal axis of crystallite is big more and a direction of principal axis is the smaller the better.But, from the angle of crystal structure, in general, carry out along with graphited, the axial big or small Lc of the c of crystallite increases, simultaneously, the axial big or small La of a also can increase, and therefore crystallite physically must be cut off on a direction of principal axis, that is to say and must pulverize.But, can not deal with problems with common breaking method.This be because, graphite is a kind of stratiform lattice structure, the preferential splitting that takes place when pulverizing with common breaking method, the pulverizing body of result's formation, the Lc of its lattice is little, La is big.
For this reason, the inventor adopts " make on a direction of principal axis fracture than the more incidental breaking method of peeling off on the c direction of principal axis " that the graphitized carbon cellulosic material block after the heat treatment is pulverized.Here said " make on a direction of principal axis fracture than the more incidental breaking method of peeling off on the c direction of principal axis ", so long as the Lc that can be ground into crystallite more than 100nm, La can be suitable for less than the breaking method of 100nm, the various forms of pulverizers of impact grinder etc. can use, and can use separately also to be used in combination.In addition,, can alleviate the live load of pulverizer if before sending into pulverizer, in advance graphitized carbon cellulosic material block is cooled off, both economical like this.At this moment, if cool off with liquid nitrogen, the axial fracture of a is very easy to take place, the Lc of therefore can be easily and obtaining crystallite reliably is more than 100nm, the crushed material of La below 100nm, and can further alleviate the live load of pulverizer, thereby be a kind of preferred scheme.
The boron compound that in lithium secondary battery cathode material of the present invention, adds, very big for the wholesome effect of the crystal structure of carbon materials, and have specificity, be illustrated below at this point.As everyone knows, boron is one of catalyst that promotes the carbon materials crystallization, and the inventor also confirms, adds, mixes the carbon materials that obtains in heat treatment more than 2400 ℃ behind the boron compound, the basal spacing d that records with X-ray diffraction
002Be 0.335nm, and the P of magnificent Lun Shi
1Value (the most contiguous hexagonal lattice plane is the probability that graphite is piled up) is 1, has desirable hexagonal crystal system graphite-structure.
Therefore, lithium secondary battery cathode material of the present invention has the advantage of graphite based material in the past, and promptly the irreversible capacity of initial stage circulation is little, and discharge potential is smooth, and density is big, therefore has high capacity.In addition, by heat-treating more than 2400 ℃, some has replaced carbon atom on the hexagonal ring boron of interpolation, makes resulting carbon materials have a kind of fault of construction in the part of being replaced by boron.
In the present invention, exist this fault of construction that produces owing to the displacement carbon atom to have great importance.That is, different in the situation of graphite layers activity with lithium, lithium become trapped in the above-mentioned defect part in the present invention.Therefore, when using this carbon materials that has captured lithium as lithium secondary battery cathode material, its discharge curve is after the same current potential flatness of demonstration and graphite, demonstrate the inclination of arriving seen in the noncrystalline cellulosic material, the promptly anti-overdischarge of one of the shortcoming that can eliminate lithium battery is poor, and the advantage with the noncrystalline based materials in the past such as residual capacity that can show battery is very desirable as lithium secondary battery cathode material.
In addition, when above-mentioned boron compound uses the oxide of boron, form small pore by its oxidation on the carbon materials surface, lithium become trapped in these pores, thereby increased the amount of collected of lithium, further improved the effective performance of lithium secondary battery cathode material.In addition, when after heat treatment, carrying out the granularity adjustment, when for example adopting liquid nitrogen to carry out special breaking method such as low-temperature grinding, the axial crystallite size Lc of c that records with X-ray diffraction is more than the 100nm, the axial crystallite size La of a is below 100nm, improve the diffusivity of lithium between the carbon element aspect, can eliminate the shortcoming of graphite based material quick charge difference.
Brief description of drawings
Fig. 1 is the list that gathers the characteristic of the various pulverizing product that obtain in expression embodiment 1, comparative example 1 and the comparative example 2, and Fig. 2 is the list of the battery behavior of these pulverizing product of expression.In addition, Fig. 3 represents the charge and discharge curve of the lithium secondary battery cathode material of embodiment 1 (c) and comparative example 1 (c) (passing through low-temperature grinding), and Fig. 4 is the decomposition diagram of the lithium secondary battery of embodiment.
The preferred embodiment of invention
Illustrate in greater detail the present invention below by embodiment and comparative example.
In 100 parts (weight) through average grain diameter after the granularity adjustment is the pitch coke of 10 μ m, add 50 parts of (weight) coal tar asphaltes, carry out mixing at 200 ℃.After its granularity is adjusted into average grain diameter 100 μ m, be converted into the B that boron mixes (a) 3% (weight) respectively
2O
3, (b) 5% (weight) B
4The B of C, (c) 10% (weight)
2O
3, (d) 20% (weight) B
4C, usefulness waits hydrostatic press (CIP) with above-mentioned each mixture press forming.Resulting block shaping thing is heat-treated (burning till) under 1000 ℃, heat-treat under 2600 ℃ then (graphitization).
Comparative example 1
In 100 parts (weight) through average grain diameter after the granularity adjustment is the pitch coke of 10 μ m, add 50 parts of (weight) coal tar asphaltes, carry out mixing at 200 ℃.After its granularity is adjusted into average grain diameter 100 μ m, be converted into the B that boron mixes (a) 2% (weight) respectively
2O
3, (b) 25% (weight) B
4C is with these two kinds of mixtures and hydrostatic press (CIP) press formings such as material usefulness that (c) do not add boron compound.Resulting block shaping thing is heat-treated (burning till) under 1000 ℃, heat-treat under 2600 ℃ then (graphitization).
Comparative example 2
Average grain diameter is in the pitch coke of 20 μ m after through the granularity adjustment, is converted into the B that boron mixes (a) 3% (weight) respectively
2O
3, (b) 5% (weight) B
4The B of C, (c) 10% (weight)
2O
3, (d) 20% (weight) B
4C puts into the crucible of graphite system respectively with these mixtures, heat-treats under 2600 ℃.
The various graphite materials that obtain in the foregoing description 1 and the comparative example 1 at room temperature and in liquid nitrogen are cooled off, be ground into average grain diameter 20 μ m then.The characteristic that gained is pulverized the pulverizing product that obtain in product and the comparative example 2 is shown among Fig. 1.In addition, there is the boron carbide (B that melts owing to fully in the powder that obtains in the comparative example 2
4C) therefore the block that produces need sieve with the sieve of 63 μ m, and shown in the figure is characteristic by the powder that obtains after the screening.In addition, also use same powder in the process of manufacturing lithium secondary battery below.
Add N-N-methyl-2-2-pyrrolidone N-(NMP) in 90 parts (weight) above-mentioned various powder and 10 parts of (weight) polyvinylidene fluoride, the furnishing pasty state is coated on the Copper Foil equably with knife coating, 150 ℃ of following vacuumizes 5 hours, removes NMP from Copper Foil.Then, use the metallic lithium foil plate, use at ethylene carbonate (EC) and 1 dissolving 1 mol LiPF in the equal-volume mixed solvent of 2-dimethoxy-ethane (DME) as to electrode and reference electrode
6The solution of (lithium hexafluoro phosphate) is as electrolyte, and the polypropylene porous film that uses ion permeability is as dividing plate, and making nonaqueous solvents is lithium secondary battery.
To this lithium secondary battery, with 0.5mA/cm
2Current density charge to 0 volt.With the quality of electric weight at this moment, as the doping capacity, represent with mAh/g with institute's value divided by employed graphite powder.Same then, with the lithium dedoping that mixes in the graphite powder, dedoping is at 0.5mA/cm
2Current density under, carry out as cut-ff voltage with 3.0V, with the quality of electric weight at this moment divided by employed graphite powder, institute's value is defined as the dedoping capacity, represent that with mAh/g the difference of obtaining doping capacity and dedoping capacity is irreversible capacity (mAh/g) and is discharging efficiency (%) with the dedoping capacity divided by doping capacity institute value.
The battery behavior of various graphite powders shown in Fig. 2.Among Fig. 3, the charge and discharge curve of the lithium secondary battery cathode material in embodiment 1 (c) and the comparative example 1 (c) (all passing through low-temperature grinding) is shown as representational example.By Fig. 1 and Fig. 2 as can be seen, adopt the lithium secondary battery cathode material that obtains among the embodiment 1, doping capacity and dedoping capacity are all very high, and irreversible capacity is less, can obtain high discharging efficiency.
In addition, as seen from Figure 3, compare with comparative example 1 (c) (graphite in the past is negative material), the lithium secondary battery cathode material that obtains among the embodiment 1 (c) has the advantage of graphite based material in the past, promptly has at 0.25V[VvsLi/Li
+] following current potential flatness, and at 1.3V[VvsLi/Li
+] more than have the discharge capacity more than 1% that is equivalent to the following discharge capacity of 0.25V, thereby can make the strong lithium secondary battery cathode material of anti-overdischarge.
The making of embodiment battery
The decomposition diagram of lithium secondary battery of the present invention shown in Fig. 4.In Fig. 4, the 1st, lithium secondary battery, the 2nd, electrode group, the 3rd, positive plate, the 4th, negative plate, the 5th, dividing plate, the 6th, battery case, the 7th, the lid of battery case, the 8th, safety valve, the 10th, positive terminal, the 11st, anodal reed.Lithium secondary battery 1 is contained in the electrode group 2 of the scroll that is made of positive plate 3, negative plate 4, dividing plate 5 and non-aqueous electrolyte in the square battery case 6 and constitutes.
In addition, positive plate 3 is connected by the terminal 10 of anodal reed 11 with the battery case lid 7 that is provided with safety valve 8 and positive terminal 10.Negative plate 4 is connected with the inwall contact of battery case 6.Lid 7 is laser-welded on the shell 6, and battery seal, the design capacity of making said structure is the battery A of 900mAh (negative plate is to obtain among the embodiment 1 (c)) and battery B (negative plate is to obtain in the comparative example 1 (c)), and electrolyte content is 25ml.
Test
To embodiment battery A and B, with the electric current of 0.5C decide electric current, constant-voltage charge reached fully charged state to 4.1 V in 5 hours.Then, in 1C with each battery discharge to 2.75V, measure discharge capacity.As a result, the discharge capacity of battery A is 890mAh, with design capacity about equally, and the discharge capacity of battery B is 700mAh, significantly is lower than design capacity.
Battery A and B further are discharged to 2.2V, in the glove box of argon atmospher, it are taken apart then, observe the situation of negative plate.As a result, battery A does not find any unusual, and the Copper Foil stripping of collector body among the battery B.
By above result as can be seen, compare with in the past battery B, battery A of the present invention has excellent discharge capacity, and at 1.3V[VvsLi/Li
+] more than have the 0-0.25V[VvsLi/Li of being equivalent to
+] the discharge capacity more than 1% of discharge capacity, thereby anti-overdischarge is strong, has high reliability and fail safe.
In addition, the structure of lithium secondary battery of the present invention has no particular limits, and can be constituted with nonaqueous electrolytic solution by anodal, negative pole and dividing plate, also can constitute by positive pole, negative pole with as the organic or inorganic solid electrolyte and the nonaqueous electrolytic solution of dividing plate.Positive active material, cell shapes and organic solvent etc. also have no particular limits, so long as use in the lithium secondary battery in the past, can obtain the effect same with the present invention.
Application on the industry
As mentioned above, negative pole of the present invention can be used as small-sized, light weight, high energy with material Metric density and the strong lithium secondary battery cathode material of anti-overdischarge.
Claims (8)
1. lithium ion secondary battery negative pole material, it is characterized in that, this material is the carbon materials block heat treatment that will contain boron or boron compound, the graphitized carbon cellulosic material of adjusting granularity, and the axial big or small Lc of the c of its crystallite is more than the 100nm, and the axial big or small La of a is below the 100nm.
2. the described lithium ion secondary battery negative pole material of claim 1 is characterized in that, the ratio that exists of the boron compound in the described graphitized carbon cellulosic material is 3-20% (weight) with boron calculating.
3. claim 1 or 2 described lithium ion secondary battery negative pole materials is characterized in that described boron compound is the oxide of boron.
4. each described lithium ion secondary battery negative pole material among the claim 1-3 is characterized in that described lithium secondary battery cathode material is at 1.3V[VvsLi/Li
+] above discharge capacity [mAh/g] is 0-0.25V[VvsLi/Li
+] more than 1% of discharge capacity [mAh/g].
5. lithium ion secondary battery negative pole is with the manufacture method of material, it is characterized in that, in carbon materials, calculate the boron compound powder that adds 3-20% (weight) with boron, the gained mixture is made piece, then in reducing atmosphere or inert gas atmosphere, heat treatment under the temperature more than 2400 ℃, adopt to make the axial fracture of a peel off more incidental breaking method resulting graphitized carbon cellulosic material block is carried out the granularity adjustment than c is axial.
6. the described lithium ion secondary battery negative pole of claim 5 is characterized in that with the manufacture method of material, and described breaking method is with described graphitized carbon cellulosic material piece cooling, to pulverize then in advance.
7. the described lithium ion secondary battery negative pole of claim 6 is characterized in that with the manufacture method of material, and described breaking method is, with liquid nitrogen described graphitized carbon cellulosic material piece is cooled off in advance, pulverizes then.
8. lithium rechargeable battery is characterized in that, each described negative pole uses material as negative electrode active material among the use claim 1-4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97196220A CN1225196A (en) | 1996-05-07 | 1997-05-07 | Cathode material for lithium ion secondary battery, method for manufacturing the same, and lithium ion secondary battery using the same |
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|---|---|---|---|
| JP137491/96 | 1996-05-07 | ||
| CN97196220A CN1225196A (en) | 1996-05-07 | 1997-05-07 | Cathode material for lithium ion secondary battery, method for manufacturing the same, and lithium ion secondary battery using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100385719C (en) * | 2004-06-11 | 2008-04-30 | 肇庆市风华锂电池有限公司 | Lithium ion secondary battery negative pole material, producing method thereof and obtained battery |
| CN102339999A (en) * | 2010-07-14 | 2012-02-01 | 中国科学院物理研究所 | Polyanion composite material, its preparation method and application |
| CN103975469A (en) * | 2011-11-24 | 2014-08-06 | 三菱商事株式会社 | Negative-electrode material for nonaqueous electrolyte secondary battery, and method for producing same |
| CN109306551A (en) * | 2018-07-18 | 2019-02-05 | 湘潭大学 | A kind of boron doped titanic oxide nanofiber and preparation method thereof and application as lithium ion battery negative material |
| CN114551836A (en) * | 2022-02-25 | 2022-05-27 | 蜂巢能源科技股份有限公司 | Negative electrode material, preparation method thereof, negative electrode sheet and battery |
| CN114899369A (en) * | 2022-04-08 | 2022-08-12 | 西部诚业科技发展(深圳)有限公司 | Conductive composition and preparation method thereof |
| CN117477039A (en) * | 2023-12-19 | 2024-01-30 | 宁德新能源科技有限公司 | Secondary battery and electronic device including the same |
-
1997
- 1997-05-07 CN CN97196220A patent/CN1225196A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100385719C (en) * | 2004-06-11 | 2008-04-30 | 肇庆市风华锂电池有限公司 | Lithium ion secondary battery negative pole material, producing method thereof and obtained battery |
| CN102339999A (en) * | 2010-07-14 | 2012-02-01 | 中国科学院物理研究所 | Polyanion composite material, its preparation method and application |
| CN102339999B (en) * | 2010-07-14 | 2014-02-05 | 中国科学院物理研究所 | Polyanion composite material, its preparation method and application |
| CN103975469A (en) * | 2011-11-24 | 2014-08-06 | 三菱商事株式会社 | Negative-electrode material for nonaqueous electrolyte secondary battery, and method for producing same |
| CN109306551A (en) * | 2018-07-18 | 2019-02-05 | 湘潭大学 | A kind of boron doped titanic oxide nanofiber and preparation method thereof and application as lithium ion battery negative material |
| CN114551836A (en) * | 2022-02-25 | 2022-05-27 | 蜂巢能源科技股份有限公司 | Negative electrode material, preparation method thereof, negative electrode sheet and battery |
| WO2023159863A1 (en) * | 2022-02-25 | 2023-08-31 | 蜂巢能源科技股份有限公司 | Negative electrode material and preparation method therefor, negative electrode plate and battery |
| CN114899369A (en) * | 2022-04-08 | 2022-08-12 | 西部诚业科技发展(深圳)有限公司 | Conductive composition and preparation method thereof |
| CN114899369B (en) * | 2022-04-08 | 2024-03-12 | 西部诚业科技发展(深圳)有限公司 | Conductive composition and preparation method thereof |
| CN117477039A (en) * | 2023-12-19 | 2024-01-30 | 宁德新能源科技有限公司 | Secondary battery and electronic device including the same |
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